Carbazole derivative, light-emitting element material and organic semiconductor material

ABSTRACT

An object is to provide a novel carbazole derivative that has an excellent carrier-transport property and can be suitably used for a transport layer or as a host material of a light-emitting element. Another object is to provide an organic semiconductor material and a light-emitting element material each using the carbazole derivative. As the carbazole derivative that can achieve the above objects, a carbazole derivative in which a carbazolyl group whose either 2- or 3-position of carbazole is substituted by the 4-position of a dibenzothiophene skeleton or a dibenzofuran skeleton is bonded to aromatic hydrocarbon that has 14 to 70 carbon atoms and includes a condensed tricyclic ring, a condensed tetracyclic ring, a condensed pentacyclic ring, a condensed hexacyclic ring, or a condensed heptacyclic ring has been able to be synthesized.

This application is a continuation of copending U.S. application Ser.No. 13/228,672 filed on Sep. 9, 2011 which is incorporated herein byreference.

TECHNICAL FIELD

The present invention relates to carbazole derivatives. The presentinvention further relates to light-emitting element materials andorganic semiconductor materials each using the carbazole derivative.

BACKGROUND ART

A display device using a light-emitting element (organic EL element) inwhich an organic compound is used as a light-emitting substance has beendeveloped rapidly as a next generation lighting device or display devicebecause it has advantages that such a light-emitting element can bemanufactured to be thin and lightweight, has very high response speedwith respect to an input signal, and has low power consumption.

In an organic EL element, when a voltage is applied between a pair ofelectrodes between which a light-emitting layer is interposed, electronsand holes are injected from the electrodes. The injected electrons andholes are recombined to form an excited state of a light-emittingsubstance contained in the light-emitting layer, and when the excitedstate relaxes to a ground state, light is emitted. A wavelength of lightemitted from a light-emitting substance is peculiar to thelight-emitting substance; thus, by using different types of organiccompounds as light-emitting substances, light-emitting elements whichexhibit various wavelengths, i.e., various colors can be obtained.

In a case of a display device which is expected to display images, suchas a display, at least three colors of light, i.e., red, green, and blueare required to be obtained in order to reproduce full-color images. Inthe case of a lighting device, in order to obtain high color renderingproperty, light having wavelength components thoroughly in the visiblelight region is ideally obtained. Actually, two or more kinds of lighthaving different wavelengths are mixed to be used for lightingapplication in many cases. Note that it is known that by mixing light ofthree colors, red, green, and blue, white light emission having highcolor rendering property can be obtained.

Light emitted from a light-emitting substance is peculiar to thesubstance, as described above. However, important performances as alight-emitting element, such as lifetime or power consumption, are notonly dependent on a light-emitting substance but also greatly dependenton layers other than a light-emitting layer, an element structure,properties of the light-emitting substance and a host, compatibilitybetween them, or the like. Therefore, it is true that many kinds oflight-emitting element materials are necessary in order to show thegrowth of this field. For the above-described reasons, light-emittingelement materials which have a variety of molecular structures have beenproposed (for example, see Patent Document 1).

REFERENCE Patent Document

-   [Patent Document 1] Japanese Published Patent Application No.    2007-15933

DISCLOSURE OF INVENTION

In view of the above, an object of one embodiment of the presentinvention is to provide a novel carbazole derivative that can be usedfor a transport layer or as a host material or a light-emitting materialof a light-emitting element.

Another object of one embodiment of the present invention is to providea light-emitting element material using the above novel carbazolederivative.

Another object of one embodiment of the present invention is to providean organic semiconductor material using the above novel carbazolederivative.

Another object of one embodiment of the present invention is to providea synthetic intermediate to synthesize the above novel carbazolederivative.

Note that in one embodiment of the present invention, it is onlynecessary that at least one of the above-described objects is achieved.

The present inventors have been able to synthesize a carbazolederivative in which a carbazolyl group whose 2- or 3-position ofcarbazole is substituted by the 4-position of dibenzothiophene ordibenzofuran is bonded to aromatic hydrocarbon that has 14 to 70 carbonatoms and includes a condensed tricyclic ring, a condensed tetracyclicring, a condensed pentacyclic ring, a condensed hexacyclic ring, or acondensed heptacyclic ring. Further, the present inventors have foundout that the carbazole derivative has a moderate carrier-transportproperty, the film quality is favorable, and the carbazole derivativecan be suitably used as a material of a light-emitting element and anorganic semiconductor material.

That is, one embodiment of the present invention is a carbazolederivative in which a carbazolyl group whose 2- or 3-position ofcarbazole is substituted by the 4-position of a dibenzothiopheneskeleton or a dibenzofuran skeleton is bonded to aromatic hydrocarbonthat has 14 to 70 carbon atoms and includes a condensed tricyclic ring,a condensed tetracyclic ring, a condensed pentacyclic ring, a condensedhexacyclic ring, or a condensed heptacyclic ring.

In addition, another embodiment of the present invention is a carbazolederivative in which a carbazolyl group whose either 2- or 3-position andeither 6- or 7-position of carbazole is substituted by the 4-position ofa dibenzothiophene skeleton or a dibenzofuran skeleton is bonded toaromatic hydrocarbon that has 14 to 70 carbon atoms and includes acondensed tricyclic ring, a condensed tetracyclic ring, a condensedpentacyclic ring, a condensed hexacyclic ring, or a condensedheptacyclic ring.

Note that the dibenzothiophene or dibenzofuran bonded to the carbazolylgroup may have a substituent.

Another embodiment of the present invention is a carbazole derivativerepresented by the following general formula (G0).

In the formula, Ar represents an aryl group that has 14 to 70 carbonatoms and includes a condensed tricyclic ring, a condensed tetracyclicring, a condensed pentacyclic ring, a condensed hexacyclic ring, or acondensed heptacyclic ring. In addition, R⁰ represents a grouprepresented by the following general formula (g1), and R⁸ represents anyone of hydrogen, an alkyl group having 1 to 4 carbon atoms, an arylgroup having 6 to 15 carbon atoms, and a group represented by thefollowing general formula (g2). Note that the substitution site of R⁰ isa carbon atom represented by either α or β, and the substitution site ofR⁸ is a carbon atom represented by either γ or δ.

(In the formula, X¹ represents oxygen or sulfur, and R¹ to R⁷individually represent any one of hydrogen, an alkyl group having 1 to 4carbon atoms, and an aryl group having 6 to 15 carbon atoms.)

(In the formula, X² represents oxygen or sulfur, and R⁹ to R¹⁵individually represent any one of hydrogen, an aryl group having 6 to 15carbon atoms, and an alkyl group having 1 to 4 carbon atoms.)

In addition, another embodiment of the present invention is a carbazolederivative represented by the general formula (G0) in which R⁸ is asubstituent represented by the general formula (g2). In the case whereR⁰ is bonded to the position of α, R⁸ is bonded to the position of γ,and in the case where R⁰ is bonded to the position of β, R⁸ is bonded tothe position of δ.

Another embodiment of the present invention is a carbazole derivativerepresented by the following general formula (G1).

In the formula, Ar¹ represents any one of a phenylene group, anaphthylene group, and a biphenylene group, and Ar² represents a groupthat has 14 to 30 carbon atoms and includes a condensed tricyclic ring,a condensed tetracyclic ring, a condensed pentacyclic ring, a condensedhexacyclic ring, or a condensed heptacyclic ring. In addition, n iseither 0 or 1. Note that Ar¹ may or may not have a substituent, and inthe case where Ar¹ has a substituent, the substituent is an alkyl grouphaving 1 to 4 carbon atoms. Note also that Ar² may or may not have asubstituent, and in the case where Ar² has a substituent, thesubstituent is any of an alkyl group having 1 to 4 carbon atoms and anaryl group having 6 to 15 carbon atoms. Further, R⁰ represents a grouprepresented by the following general formula (g1), and R⁸ represents anyone of hydrogen, an aryl group having 6 to 15 carbon atoms, an alkylgroup having 1 to 4 carbon atoms, and a group represented by thefollowing general formula (g2). Note that the substitution site of R⁰ isa carbon atom represented by either α or β, and the substitution site ofR⁸ is a carbon atom represented by either γ or δ.

(In the formula, X¹ represents oxygen or sulfur, and R¹ to R⁷individually represent any one of hydrogen, an alkyl group having 1 to 4carbon atoms, and an aryl group having 6 to 15 carbon atoms.)

(In the formula, X² represents oxygen or sulfur, and R⁹ to R¹⁵individually represent any one of hydrogen, an aryl group having 6 to 15carbon atoms, and an alkyl group having 1 to 4 carbon atoms.)

In addition, another embodiment of the present invention is a carbazolederivative represented by the general formula (G1) in which R⁸ is asubstituent represented by the general formula (g2). In the case whereR⁰ is bonded to the position of α, R⁸ is bonded to the position of γ,and in the case where R⁰ is bonded to the position of β, R⁸ is bonded tothe position of δ.

Another embodiment of the present invention is a carbazole derivativerepresented by the following general formula (G1).

In the formula, Ar¹ represents any one of a phenylene group, anaphthylene group, and a biphenylene group, and Ar² represents a groupthat has 14 to 30 carbon atoms and includes a condensed tricyclic ring,a condensed tetracyclic ring, a condensed pentacyclic ring, a condensedhexacyclic ring, or a condensed heptacyclic ring. In addition, n iseither 0 or 1. Note that Ar¹ may or may not have a substituent, and inthe case where Ar¹ has a substituent, the substituent is an alkyl grouphaving 1 to 4 carbon atoms. Note also that Ar² may or may not have asubstituent, and in the case where Ar² has a substituent, thesubstituent is any of an alkyl group having 1 to 4 carbon atoms and anaryl group having 6 to 15 carbon atoms. Further, R⁰ represents a grouprepresented by the following general formula (g3), and R⁸ represents anyone of hydrogen, an aryl group having 6 to 15 carbon atoms, an alkylgroup having 1 to 4 carbon atoms, and a group represented by thefollowing general formula (g4). Note that the substitution site of R⁰ isa carbon atom represented by either α or β, and the substitution site ofR⁸ is a carbon atom represented by either γ or δ.

In the formula, X¹ represents oxygen or sulfur, and R¹, R³, and R⁶individually represent any one of hydrogen, an aryl group having 6 to 15carbon atoms, and an alkyl group having 1 to 4 carbon atoms.

Note that in the formula, X² represents oxygen or sulfur, and R⁹, R¹¹,and R¹⁴ individually represent any one of hydrogen, an aryl group having6 to 15 carbon atoms, and an alkyl group having 1 to 4 carbon atoms.

Another embodiment of the present invention is a carbazole derivativehaving any of the above structures in which R⁸ is hydrogen or a grouprepresented by the following general formula (g4).

In addition, another embodiment of the present invention is a carbazolederivative that has any of the above structures and is represented bythe general formula (G1) in which R⁸ is a substituent represented by thegeneral formula (g4). In the case where R⁰ is bonded to the position ofα, R⁸ is bonded to the position of γ, and in the case where R⁰ is bondedto the position of β, R⁸ is bonded to the position of δ.

Another embodiment of the present invention is a carbazole derivativerepresented by the following general formula (G1).

In the formula, Ar¹ represents any one of a phenylene group, anaphthylene group, and a biphenylene group, and Ar² represents a groupthat has 14 to 30 carbon atoms and includes a condensed tricyclic ring,a condensed tetracyclic ring, a condensed pentacyclic ring, a condensedhexacyclic ring, or a condensed heptacyclic ring. In addition, n iseither 0 or 1. Note that Ar¹ may or may not have a substituent, and inthe case where Ar¹ has a substituent, the substituent is an alkyl grouphaving 1 to 4 carbon atoms. Note also that Ar² may or may not have asubstituent, and in the case where Ar² has a substituent, thesubstituent is any of an alkyl group having 1 to 4 carbon atoms and anaryl group having 6 to 15 carbon atoms. Further, R⁰ represents a grouprepresented by the following general formula (g5), and R⁸ representshydrogen or a group represented by the following general formula (g6).Note that the substitution site of R⁰ is a carbon atom represented byeither α or β, and the substitution site of R⁸ is a carbon atomrepresented by either γ or δ.

In the formula, X¹ represents oxygen or sulfur.

(In the formula, X² represents oxygen or sulfur.)

In addition, another embodiment of the present invention is a carbazolederivative that has any of the above structures and is represented bythe general formula (G1) in which R⁸ is a substituent represented by thegeneral formula (g6). In the case where R⁰ is bonded to the position ofα, R⁸ is bonded to the position of γ, and in the case where R⁰ is bondedto the position of β, R⁸ is bonded to the position of δ.

Another embodiment of the present invention is a carbazole derivativerepresented by the following general formula (G2).

Note that in the formula, X represents oxygen or sulfur, Ar¹ representsany one of a phenylene group, a naphthylene group, and a biphenylenegroup, and Ar² represents a group that has 14 to 30 carbon atoms andincludes a condensed tricyclic ring, a condensed tetracyclic ring, acondensed pentacyclic ring, a condensed hexacyclic ring, or a condensedheptacyclic ring. In addition, n is either 0 or 1. Note that Ar¹ may ormay not have a substituent, and in the case where Ar¹ has a substituent,the substituent is an alkyl group having 1 to 4 carbon atoms. Note alsothat Ar² may or may not have a substituent, and in the case where Ar²has a substituent, the substituent is any of an alkyl group having 1 to4 carbon atoms and an aryl group having 6 to 15 carbon atoms.

Another embodiment of the present invention is a carbazole derivativerepresented by the following general formula (G3).

Note that in the formula, X¹ and X² individually represent oxygen orsulfur, Ar¹ represents any one of a phenylene group, a naphthylenegroup, and a biphenylene group, and Ar² represents a group that has 14to 30 carbon atoms and includes a condensed tricyclic ring, a condensedtetracyclic ring, a condensed pentacyclic ring, a condensed hexacyclicring, or a condensed heptacyclic ring. In addition, n is either 0 or 1.Note that Ar¹ may or may not have a substituent, and in the case whereAr¹ has a substituent, the substituent is an alkyl group having 1 to 4carbon atoms. Note also that Ar² may or may not have a substituent, andin the case where Ar² has a substituent, the substituent is any of analkyl group having 1 to 4 carbon atoms and an aryl group having 6 to 15carbon atoms.

Another embodiment of the present invention is a carbazole derivativerepresented by the following general formula (G4).

Note that in the formula, X¹ and X² individually represent oxygen orsulfur, Ar¹ represents any one of a phenylene group, a naphthylenegroup, and a biphenylene group, and Ar² represents a group that has 14to 30 carbon atoms and includes a condensed tricyclic ring, a condensedtetracyclic ring, a condensed pentacyclic ring, a condensed hexacyclicring, or a condensed heptacyclic ring. In addition, n is either 0 or 1.Note that Ar¹ may or may not have a substituent, and in the case whereAr¹ has a substituent, the substituent is an alkyl group having 1 to 4carbon atoms. Note also that Ar² may or may not have a substituent, andin the case where Ar² has a substituent, the substituent is any of analkyl group having 1 to 4 carbon atoms and an aryl group having 6 to 15carbon atoms.

Another embodiment of the present invention is a carbazole derivativerepresented by the following structural formula.

Another embodiment of the present invention is a carbazole derivativerepresented by the following structural formula.

Another embodiment of the present invention is a carbazole derivativerepresented by the following structural formula.

Another embodiment of the present invention is a carbazole derivativerepresented by the following structural formula.

Another embodiment of the present invention is a carbazole derivativerepresented by the following structural formula.

Another embodiment of the present invention is a carbazole derivativerepresented by the following structural formula.

In addition, another embodiment of the present invention is a syntheticintermediate to synthesize any of the above carbazole derivatives. Thatis, another embodiment of the present invention is a carbazolederivative represented by the following general formula (G5).

(In the formula, R⁰ represents a group represented by the followinggeneral formula (g1), and R⁸ represents any one of hydrogen, an alkylgroup having 1 to 4 carbon atoms, an aryl group having 6 to 15 carbonatoms, and a group represented by the following general formula (g2).Note that the substitution site of R⁰ is a carbon atom represented byeither α or β, and the substitution site of R⁸ is a carbon atomrepresented by either γ or δ.)

(In the formula, X¹ represents oxygen or sulfur, and R¹ to R⁷individually represent any one of hydrogen, an alkyl group having 1 to 4carbon atoms, and an aryl group having 6 to 15 carbon atoms.)

(In the formula, X² represents oxygen or sulfur, and R⁹ to R¹⁵individually represent any one of hydrogen, an aryl group having 6 to 15carbon atoms, and an alkyl group having 1 to 4 carbon atoms.)

In addition, another embodiment of the present invention is a carbazolederivative that has any of the above structures and is represented bythe general formula (G5) in which R⁸ is a substituent represented by thegeneral formula (g2). In the case where R⁰ is bonded to the position ofα, R⁸ is bonded to the position of γ, and in the case where R⁰ is bondedto the position of β, R⁸ is bonded to the position of δ.

Another embodiment of the present invention is a carbazole derivativerepresented by the following general formula (G5).

(In the formula, R⁰ represents a group represented by the followinggeneral formula (g3), and R⁸ represents any one of hydrogen, an arylgroup having 6 to 15 carbon atoms, an alkyl group having 1 to 4 carbonatoms, and a group represented by the following general formula (g4).Note that the substitution site of R⁰ is a carbon atom represented byeither α or β, and the substitution site of R⁸ is a carbon atomrepresented by either γ or δ.)

(In the formula, X¹ represents oxygen or sulfur, and R¹, R³, and R⁶individually represent any one of hydrogen, an aryl group having 6 to 15carbon atoms, and an alkyl group having 1 to 4 carbon atoms.)

(Note that in the formula, X² represents oxygen or sulfur, and R⁹, R¹¹,and R¹⁴ individually represent any one of hydrogen, an aryl group having6 to 15 carbon atoms, and an alkyl group having 1 to 4 carbon atoms.)

In addition, another embodiment of the present invention is a carbazolederivative that has any of the above structures and is represented bythe general formula (G5) in which R⁸ is a substituent represented by thegeneral formula (g4). In the case where R⁰ is bonded to the position ofα, R⁸ is bonded to the position of γ, and in the case where R⁰ is bondedto the position of β, R⁸ is bonded to the position of δ.

Another embodiment of the present invention is a carbazole derivativerepresented by the following general formula (G5).

(In the formula, R⁰ represents a group represented by the followinggeneral formula (g3), and R⁸ represents hydrogen or a group representedby the following general formula (g4). Note that the substitution siteof R⁰ is a carbon atom represented by either α or β, and thesubstitution site of R⁸ is a carbon atom represented by either γ or δ.)

(In the formula, X¹ represents oxygen or sulfur, and R¹, R³, and R⁶individually represent any one of hydrogen, an aryl group having 6 to 15carbon atoms, and an alkyl group having 1 to 4 carbon atoms.)

(Note that in the formula, X² represents oxygen or sulfur, and R⁹, R¹¹,and R¹⁴ individually represent any one of hydrogen, an aryl group having6 to 15 carbon atoms, and an alkyl group having 1 to 4 carbon atoms.)

In addition, another embodiment of the present invention is a carbazolederivative that has any of the above structures and is represented bythe general formula (G5) in which R⁸ is a substituent represented by thegeneral formula (g4). In the case where R⁰ is bonded to the position ofα, R⁸ is bonded to the position of γ, and in the case where R⁰ is bondedto the position of β, R⁸ is bonded to the position of δ.

Another embodiment of the present invention is a carbazole derivativerepresented by the following general formula (G5).

(In the formula, R⁰ represents a group represented by the followinggeneral formula (g5), and R⁸ represents hydrogen or a group representedby the following general formula (g6). Note that the substitution siteof R⁰ is a carbon atom represented by either α or β, and thesubstitution site of R⁸ is a carbon atom represented by either γ or δ.)

(In the formula, X¹ represents oxygen or sulfur.)

(In the formula, X² represents oxygen or sulfur.)

In addition, another embodiment of the present invention is a carbazolederivative that has any of the above structures and is represented bythe general formula (G5) in which R⁸ is a substituent represented by thegeneral formula (g6). In the case where R⁰ is bonded to the position ofα, R⁸ is bonded to the position of γ, and in the case where R⁰ is bondedto the position of β, R⁸ is bonded to the position of δ.

Another embodiment of the present invention is a carbazole derivativerepresented by the following general formula (G6).

(Note that in the formula, X represents oxygen or sulfur.)

Another embodiment of the present invention is a carbazole derivativerepresented by the following general formula (G7).

(Note that in the formula, X¹ and X² individually represent oxygen orsulfur.)

Another embodiment of the present invention is a carbazole derivativerepresented by the following general formula (G8).

(Note that in the formula, X¹ and X² individually represent oxygen orsulfur.)

Another embodiment of the present invention is a carbazole derivativerepresented by the following structural formula.

Another embodiment of the present invention is a carbazole derivativerepresented by the following structural formula.

Another embodiment of the present invention is a carbazole derivativerepresented by the following structural formula.

Another embodiment of the present invention is a carbazole derivativerepresented by the following structural formula.

Another embodiment of the present invention is a carbazole derivativerepresented by the following structural formula.

A carbazole derivative having any of the above-described structures is alight-emitting element material having a wide energy gap, and can beused for a transport layer or as a host material or a light-emittingsubstance of the light-emitting element. A light-emitting element usinga light-emitting element material containing the carbazole derivativecan be a light-emitting element having high emission efficiency. Inaddition, a light-emitting element using a light-emitting elementmaterial containing the carbazole derivative can be a light-emittingelement driven with a low driving voltage. Further, a light-emittingelement using a light-emitting element material containing the carbazolederivative can be a light-emitting element having a long lifetime. Thecarbazole derivative can also be used as an organic semiconductormaterial.

In addition, a synthetic intermediate used for synthesis of the abovecarbazole derivative can be provided.

BRIEF DESCRIPTION OF DRAWINGS

FIGS. 1A and 1B are conceptual diagrams of light-emitting elements.

FIG. 2 is a conceptual diagram of an organic semiconductor element.

FIGS. 3A and 3B are conceptual diagrams of an active matrixlight-emitting device.

FIGS. 4A and 4B are conceptual diagrams of a passive matrixlight-emitting device.

FIGS. 5A to 5D each illustrate an electronic device.

FIG. 6 illustrates an electronic device.

FIG. 7 illustrates a lighting device.

FIG. 8 illustrates lighting devices.

FIGS. 9A and 9B are ¹H NMR charts of DBTCz-II.

FIG. 10 is a ¹H NMR chart of DBTCzPA-II.

FIGS. 11A and 11B show absorption spectra and emission spectra ofDBTCzPA-II.

FIGS. 12A and 12B are ¹H NMR charts of DBFCz-II.

FIG. 13 is a ¹H NMR chart of DBFCzPA-II.

FIGS. 14A and 14B show absorption spectra and emission spectra ofDBFCzPA-II.

FIGS. 15A and 15B are ¹H NMR charts of DBTCzTp-II.

FIGS. 16A and 16B show absorption spectra and emission spectra ofDBTCzTp-II.

FIGS. 17A and 17B are ¹H NMR charts of DBFCzTp-II.

FIGS. 18A and 18B show absorption spectra and emission spectra ofDBFCzTp-II.

FIGS. 19A and 19B are ¹H NMR charts of 2DBFCzPA-II.

FIGS. 20A and 20B are ¹H NMR charts of DBT2Cz-II.

FIGS. 21A and 21B are ¹H NMR charts of DBT2CzPA-II.

FIGS. 22A and 22B are ¹H NMR charts of DBF2Cz-II.

FIG. 23 is a graph showing luminance vs. current density characteristicsof a light-emitting element 1 and a light-emitting element 2.

FIG. 24 is a graph showing luminance vs. voltage characteristics of thelight-emitting element 1 and the light-emitting element 2.

FIG. 25 is a graph showing current efficiency vs. luminancecharacteristics of the light-emitting element 1 and the light-emittingelement 2.

FIG. 26 shows emission spectra of the light-emitting element 1 and thelight-emitting element 2.

FIG. 27 is a graph showing change of normalized luminance vs. timecharacteristics of the light-emitting element 1 and the light-emittingelement 2.

FIG. 28 is a graph showing luminance vs. current density characteristicsof a light-emitting element 3 and a light-emitting element 4.

FIG. 29 is a graph showing luminance vs. voltage characteristics of thelight-emitting element 3 and the light-emitting element 4.

FIG. 30 is a graph showing current efficiency vs. luminancecharacteristics of the light-emitting element 3 and the light-emittingelement 4.

FIG. 31 shows emission spectra of the light-emitting element 3 and thelight-emitting element 4.

FIG. 32 is a graph showing change of normalized luminance vs. timecharacteristics of the light-emitting element 3 and the light-emittingelement 4.

FIGS. 33A and 33B are ¹H NMR charts of 2DBTCzPA-II.

FIGS. 34A and 34B show absorption spectra and emission spectra of2DBTCzPA-II.

FIGS. 35A and 35B are ¹H NMR charts of 2DBFCzPA-II.

FIGS. 36A and 36B show absorption spectra and emission spectra of2DBFCzPA-II.

FIGS. 37A and 37B are ¹H NMR charts of mDBTCzPA-II.

FIGS. 38A and 38B show absorption spectra and emission spectra ofmDBTCzPA-II.

FIGS. 39A and 39B are ¹H NMR charts of mDBFCzPA-II.

FIGS. 40A and 40B show absorption spectra and emission spectra ofmDBFCzPA-II.

FIGS. 41A and 41B are ¹H NMR charts of DBTCz-IV.

FIGS. 42A and 42B are ¹H NMR charts of DBTCzTp-IV.

FIGS. 43A and 43B show absorption spectra and emission spectra ofDBTCzTp-IV.

FIGS. 44A and 44B are ¹H NMR charts of 2DBTCzPPA-II.

FIGS. 45A and 45B show absorption spectra and emission spectra of2DBTCzPPA-II.

FIGS. 46A and 46B are ¹H NMR charts of 2DBFCzPPA-II.

FIGS. 47A and 47B show absorption spectra and emission spectra of2DBFCzPPA-II.

FIGS. 48A and 48B are ¹H NMR charts of 2mDBTCzPPA-II.

FIGS. 49A and 49B show absorption spectra and emission spectra of2mDBTCzPPA-II.

FIGS. 50A and 50B are ¹H NMR charts of 2mDBFCzPPA-II.

FIGS. 51A and 51B show absorption spectra and emission spectra of2mDBFCzPPA-II.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments of the present invention are described. It iseasily understood by those skilled in the art that modes and detailsdisclosed herein can be modified in various ways without departing fromthe spirit and the scope of the present invention. Therefore, thepresent invention is not construed as being limited to description ofthe embodiments.

(Embodiment 1)

A carbazole derivative in this embodiment is a substance in which acarbazolyl group whose carbon atom at the 2- or 3-position of carbazoleis substituted by a carbon atom at the 4-position of dibenzothiophene orthe 4-position of dibenzofuran is bonded to aromatic hydrocarbon having14 to 70 carbon atoms. Note that the dibenzothiophene or dibenzofuranand the carbazole may or may not have a substituent. In addition, thearomatic hydrocarbon has a structure that includes a condensed tricyclicring, a condensed tetracyclic ring, a condensed pentacyclic ring, acondensed hexacyclic ring, or a condensed heptacyclic ring, and thenumber of carbon atoms of the aromatic hydrocarbon indicates the totalnumber of carbon atoms, including those of a substituent such as analkyl group.

In the case where the dibenzothiophene or dibenzofuran bonded to thecarbazolyl group has a substituent, the substituent can be any of anaryl group having 6 to 15 carbon atoms and an alkyl group having 1 to 4carbon atoms.

In the case where the carbazole in the carbazolyl group has anothersubstituent, the substitution site of the substituent is the 6- or7-position of the carbazole, and the substituent can be any of an arylgroup having 6 to 15 carbon atoms, an alkyl group having 1 to 4 carbonatoms, a dibenzothiophen-4-yl group, and a dibenzofuran-4-yl group. Inthe case where the dibenzothiophen-4-yl group or dibenzofuran-4-yl groupis selected as the substituent that is bonded to the 6- or 7-position ofthe carbazole, the dibenzothiophen-4-yl group or the dibenzofuran-4-ylgroup may further have a substituent that can be selected from an arylgroup having 6 to 15 carbon atoms and an alkyl group having 1 to 4carbon atoms. For easier synthesis, in the case where thedibenzothiophen-4-yl group or dibenzofuran-4-yl group is selected as thesubstituent that is bonded to the 6- or 7-position of the carbazole andthe dibenzothiophene or the dibenzofuran is bonded to the 2-position ofthe carbazole, the dibenzothiophen-4-yl group or the dibenzofuran-4-ylgroup is preferably substituted at the 7-position of the carbazole; inthe case where the dibenzothiophene or the dibenzofuran is bonded to the3-position of the carbazole, the dibenzothiophen-4-yl group or thedibenzofuran-4-yl group is preferably substituted at the 6-position ofthe carbazole. Note that for easier synthesis, the dibenzothiophene ordibenzofuran bonded to the 2- or 3-position of the carbazole and thesubstituent bonded to the 6- or 7-position of the carbazole arepreferably of the same type.

The present inventors have found out that the above-described carbazolederivative has a moderate carrier-transport property and can be suitablyused as a light-emitting element material. With the use of thelight-emitting element material having excellent carrier mobility, alight-emitting element driven with a low driving voltage can beprovided.

The above-described carbazole derivative has a rigid group such asdibenzothiophene or dibenzofuran, and thus the morphology is excellentand the film quality is stable. Further, the thermophysical property isalso excellent. From the above, a light-emitting element that uses alight-emitting material containing the carbazole derivative can be alight-emitting element having a long lifetime.

Note that with a substance having an electron-transport propertyselected as the above-described aromatic hydrocarbon that includes acondensed tricyclic ring, a condensed tetracyclic ring, a condensedpentacyclic ring, a condensed hexacyclic ring, or a condensedheptacyclic ring, a material having both the electron-transport propertyand a hole-transport property, i.e., a bipolar material, can beobtained. With the use of the bipolar material for a light-emittinglayer in a light-emitting element, localization of an emission regioncan be prevented, concentration quenching or triplet-tripletannihilation (T-T annihilation) can be suppressed, and a light-emittingelement having high emission efficiency can be obtained. From such apoint of view, it is preferable to select anthracene, pyrene, chrysene,naphthacene, pentacene, fluoranthene, perylene, coronene, ortriphenylene as the condensed tricyclic ring, the condensed tetracyclicring, the condensed pentacyclic ring, the condensed hexacyclic ring, orthe condensed heptacyclic ring.

In addition, a skeleton whose T1 level is high, such as triphenylene orphenanthrene, can be used as the condensed tricyclic ring, the condensedtetracyclic ring, the condensed pentacyclic ring, the condensedhexacyclic ring, or the condensed heptacyclic ring for suitableapplication to a phosphorescent element.

The above-described carbazole derivative can be represented by thefollowing general formula (G0) or (G1).

In the formula (G0), Ar represents an aryl group that has 14 to 70carbon atoms. Note that the aromatic hydrocarbon has a structure thatincludes a condensed tricyclic ring, a condensed tetracyclic ring, acondensed pentacyclic ring, a condensed hexacyclic ring, or a condensedheptacyclic ring, and the number of carbon atoms of the aromatichydrocarbon indicates the total number of carbon atoms, including thoseof a substituent such as an alkyl group.

In the formula (G1), Ar¹ represents any one of a phenylene group, anaphthylene group, and a biphenylene group, and Ar² represents a groupthat has 14 to 30 carbon atoms and includes a condensed tricyclic ring,a condensed tetracyclic ring, a condensed pentacyclic ring, a condensedhexacyclic ring, or a condensed heptacyclic ring. In addition, n iseither 0 or 1. Note that Ar¹ may or may not have a substituent, and inthe case where Ar¹ has a substituent, the substituent is an alkyl grouphaving 1 to 4 carbon atoms. Note also that Ar² may or may not have asubstituent, and in the case where Ar² has a substituent, thesubstituent is any of an alkyl group having 1 to 4 carbon atoms and anaryl group having 6 to 15 carbon atoms.

A carbazole derivative represented by the above general formula (G0) or(G1) in which Ar is such a group has excellent morphology and the filmquality is stable. Further, the thermophysical property is alsoexcellent.

Note that it is found out that a substance that has a favorable balanceof the electron-transport property and the hole-transport property, andcan be very effective as a light-emitting element material can beobtained by including anthracene such as diphenylanthracene in Ar in thegeneral formula (G0) or Ar² in the general formula (G1).

In addition, with a skeleton that has a chromophore, such as anthracene,pyrene, chrysene, naphthacene, pentacene, fluoranthene, perylene, orcoronene, as Ar in the general formula (G0) or Ar² in the generalformula (G1), a light-emitting element material having a favorablecarrier balance and high efficiency can be obtained. In addition, askeleton whose T1 level is high, such as triphenylene or phenanthrene,can be used as Ar to obtain a light-emitting element material forsuitable application to a phosphorescent element.

R⁰ represents a group represented by the following general formula (g1).Note that the substitution site of R⁰ is a carbon atom represented byeither α or β.

In the formula (g1), X¹ represents oxygen or sulfur, and R¹ to R⁷individually represent any one of hydrogen, an alkyl group having 1 to 4carbon atoms, and an aryl group having 6 to 15 carbon atoms.

Further, a carbazole derivative having the above-described structure hasan excellent carrier-transport property, and a light-emitting elementusing the carbazole derivative can be a light-emitting element drivenwith a low driving voltage. In addition, the above-described carbazolederivative has a rigid group such as dibenzothiophene or dibenzofuran,and thus the morphology is excellent and the film quality is stable.Further, the thermophysical property is also excellent. From the above,by using a light-emitting material using the carbazole derivative, alight-emitting element having a long lifetime can be provided.

Note that the carbazole derivative represented by the above generalformula (G1) may have a substituent represented by R⁸, as alsoillustrated in the above general formula (G1). R⁸ represents any one ofhydrogen, an alkyl group having 1 to 4 carbon atoms, an aryl grouphaving 6 to 15 carbon atoms, and a group represented by the followinggeneral formula (g2). Note that the substitution site of R⁸ is a carbonatom represented by either γ or δ.

In the formula (g2), X² represents oxygen or sulfur, and R⁹ to R¹⁵individually represent any one of hydrogen, an aryl group having 6 to 15carbon atoms, and an alkyl group having 1 to 4 carbon atoms.

In the case where R⁸ is a substituent other than hydrogen, R⁸ and R⁰ arepreferably the same group for easier synthesis.

In the case where the group represented by the above general formula(g1) further includes a substituent, the substitution site of thesubstituent is preferably a site represented by R¹, R³, or R⁶ for areduction in cost of synthesizing the material owing to availability ofthe material and easiness of the synthesis. From the same point of view,it is further preferable that R¹ to R⁷ be all hydrogen.

In a similar manner, in the case where the group represented by (g2) isapplied as R⁸, the substitution site of the substituent is preferably asite represented by R⁹, R¹¹, or R¹⁴, and it is further preferable thatR⁹ to R¹⁵ be all hydrogen.

In the above general formula (G0) or (G1), as an alkyl group having 1 to4 carbon atoms or an aryl group having 6 to 15 carbon atoms, which canbe used as any of R¹ to R¹⁵, any of the groups represented by thefollowing structural formulas (R-1) to (R-23) can be used. Note that asR⁸, instead of the groups represented by the following structuralformulas (R-1) to (R-23), the group represented by the above generalformula (g2) can be used.

In the above general formula (G0), as an aryl group having 14 to 70carbon atoms, which can be applied to Ar, any of the groups representedby the following structural formulas (Ar-1) to (Ar-78) can be used. Notethat an —Ar group in the general formula (G0) corresponds to an—(Ar¹)n-Ar² group in the general formula (G1) (note that Ar¹ is aphenylene group, a naphthylene group, or a biphenylene group, and n is 0or 1).

As specific structures of the carbazole derivative represented by theabove general formula (G0) or (G1), substances represented by thefollowing structural formulas (100) to (441) and (500) to (841) and thelike can be given.

The above-described carbazole derivative is suitable as acarrier-transport material or a host material because thecarrier-transport property is excellent. Owing to this, a light-emittingelement driven with a low driving voltage can also be provided. Inaddition, any of the carbazole derivatives in this embodiment has arigid group such as dibenzothiophene or dibenzofuran, and thus themorphology is excellent and the film quality is stable. Further, thethermophysical property is also excellent. From the above, alight-emitting element using such a carbazole derivative can be alight-emitting element having a long lifetime. In addition, with askeleton that has a chromophore, such as anthracene, pyrene, chrysene,naphthacene, pentacene, fluoranthene, perylene, or coronene, alight-emitting element material having high efficiency can be obtained.Further, a skeleton whose T1 level is high, such as triphenylene orphenanthrene, can be used as Ar to obtain a light-emitting elementmaterial for suitable application to a phosphorescent element.

(Embodiment 2)

Next, in this embodiment, a method for synthesizing a carbazolederivative represented by the following general formula (G0) or (G1) isdescribed.

In the formula (G0), Ar represents an aryl group that has 14 to 70carbon atoms and includes a condensed tricyclic ring, a condensedtetracyclic ring, a condensed pentacyclic ring, a condensed hexacyclicring, or a condensed heptacyclic ring. In addition, in the formula (G1),Ar¹ represents any one of a phenylene group, a naphthylene group, and abiphenylene group, and Ar² represents a group that has 14 to 30 carbonatoms and includes a condensed tricyclic ring, a condensed tetracyclicring, a condensed pentacyclic ring, a condensed hexacyclic ring, or acondensed heptacyclic ring. In addition, n is either 0 or 1. Note thatAr¹ may or may not have a substituent, and in the case where Ar¹ has asubstituent, the substituent is an alkyl group having 1 to 4 carbonatoms. Note also that Ar² may or may not have a substituent, and in thecase where Ar² has a substituent, the substituent is any of an alkylgroup having 1 to 4 carbon atoms and an aryl group having 6 to 15 carbonatoms. Further, in the carbazole derivative represented by the generalformula (G1), the Ar group in the general formula (G0) is represented byan (Ar¹)n-Ar² group.

In addition, R⁰ is a substituent represented by the following generalformula (g1) which is bonded to a carbon atom represented by either α orβ. R⁸ represents any one of hydrogen, an alkyl group having 1 to 4carbon atoms, an aryl group having 6 to 15 carbon atoms, and a grouprepresented by the following general formula (g2), which is bonded to acarbon atom represented by either γ or δ.

In the formula, X¹ represents oxygen or sulfur, and R¹ to R⁷individually represent any one of hydrogen, an alkyl group having 1 to 4carbon atoms, and an aryl group having 6 to 15 carbon atoms.

In the formula (g2), X² represents oxygen or sulfur, and R⁹ to R¹⁵individually represent any one of hydrogen, an aryl group having 6 to 15carbon atoms, and an alkyl group having 1 to 4 carbon atoms.

Here, as described above, the Ar group in the general formula (G0) isthe (Ar¹)n-Ar² group in the general formula (G1), and R⁰ in the formulasis a substituent represented by the above general formula (g1);therefore, the above general formulas (G0) and (G1) can also berepresented by the following general formula (G1′). In the generalformula (G1′), the substitution site of the substituent corresponding tothe above general formula (g1) is a carbon atom represented by either αor β in the general formula (G0) or (G1). Hereinafter, the substitutionsites of substituents or elements represented by Ar, R¹ to R¹⁶, X¹, andX², and substituents corresponding to R⁸ and the above general formula(g1) are the same as those in the above explanation unless otherwiseexplained.

In this embodiment, a method for synthesizing substances represented bythe above general formula (G1′) is described by using the generalformula (GP) instead of the general formula (G0) or (G1).

<Synthesis Method 1>

In Synthesis Method 1, a method for synthesizing a substance representedby the general formula (G1′) in which R⁸ is hydrogen (the followinggeneral formula (G1′-1)) is described.

First, a compound having a halogen group or a triflate group at the 2-or 3-position of 9H-carbazole (a compound 1) is coupled with a boronicacid compound of dibenzothiophene or a boronic acid compound ofdibenzofuran (a compound 2), whereby a 9H-carbazole derivative having astructure in which the 2- or 3-position of 9H-carbazole is bonded to the4-position of dibenzothiophene or the 4-position of dibenzofuran (acompound 3) can be obtained (a reaction formula (A-1)).

In the reaction formula (A-1), X¹ represents oxygen or sulfur, X³represents a halogen group, a triflate group, or the like, X⁴ representsa boronic acid (the boronic acid may be protected by ethylene glycol orthe like), R¹ to R⁷ individually represent any one of hydrogen, an alkylgroup having 1 to 4 carbon atoms, and an aryl group having 6 to 15carbon atoms. As the coupling reaction in the reaction formula (A-1), aSuzuki-Miyaura coupling reaction using a palladium catalyst or the likecan be given.

Next, the obtained 9H-carbazole derivative (the compound 3) is coupledwith a halogenated aryl (a compound 4), whereby a compound (G1′-1),which is the object of the synthesis, can be obtained (a reactionformula (A-2)).

In the reaction formula (A-2), X¹ represents oxygen or sulfur, X⁵represents a halogen group or the like, R¹ to R⁷ individually representany one of hydrogen, an alkyl group having 1 to 4 carbon atoms, and anaryl group having 6 to 15 carbon atoms, and Ar represents an aryl groupthat has 14 to 70 carbon atoms and includes a condensed tricyclic ring,a condensed tetracyclic ring, a condensed pentacyclic ring, a condensedhexacyclic ring, or a condensed heptacyclic ring. As the couplingreaction in the reaction formula (A-2), a Buchwald-Hartwig reactionusing a palladium catalyst, an Ullmann reaction using copper or a coppercompound, or the like can be given.

<Synthesis Method 2>

In Synthesis Method 2, a method for synthesizing a substance in which R⁸in the above general formula (G1′) is a substituent represented by theabove general formula (g2) (the following general formula (G1′-2)) isdescribed.

First, a carbazole derivative having halogen groups at the 2- and7-positions of, the 3- and 6-positions of, or the 2- and 6-positions of9H-carbazole (a compound 5) is coupled with a boronic acid compound ofdibenzothiophene or a boronic acid compound of dibenzofuran (a compound2), whereby a carbazole derivative (a compound 6) can be obtained (areaction formula (B-1)).

In the reaction formula (B-1), X⁶ and X⁷ individually represent ahalogen group, a triflate group, or the like, X⁴ represents a boronicacid (the boronic acid may be protected by ethylene glycol or the like),R¹ to R⁷ individually represent any of hydrogen, an alkyl group having 1to 4 carbon atoms, and an aryl group having 6 to 15 carbon atoms. X⁶ andX⁷ may the same or different. As the coupling reaction in the reactionformula (B-1), a Suzuki-Miyaura coupling reaction using a palladiumcatalyst or the like can be given.

Next, the monohalide of 9H-carbazole (the compound 6) is coupled with aboronic acid compound of dibenzothiophene or a boronic acid compound ofdibenzofuran (a compound 7), whereby a carbazole derivative (a compound8) can be obtained (a reaction formula (B-2)).

In the reaction formula (B-2), X⁶ represents a halogen group, a triflategroup, or the like, X⁸ represents a boronic acid (the boronic acid maybe protected by ethylene glycol or the like), R¹ to R⁷ individuallyrepresent any of hydrogen, an alkyl group having 1 to 4 carbon atoms,and an aryl group having 6 to 15 carbon atoms. As the coupling reactionin the reaction formula (B-1), a Suzuki-Miyaura coupling reaction usinga palladium catalyst or the like can be given.

Lastly, the 9H-carbazole derivative (the compound 8) is coupled with ahalogenated aryl (a compound 4), whereby a compound (G1′-2), which isthe object of the synthesis, can be obtained (a reaction formula (B-3)).

In the reaction formula (B-3), X¹ and X² individually represents oxygenor sulfur, X⁵ represents a halogen group, R¹ to R⁷ individuallyrepresent any one of hydrogen, an alkyl group having 1 to 4 carbonatoms, and an aryl group having 6 to 15 carbon atoms, and Ar representsan aryl group that has 14 to 70 carbon atoms and includes a condensedtricyclic ring, a condensed tetracyclic ring, a condensed pentacyclicring, a condensed hexacyclic ring, or a condensed heptacyclic ring. Asthe coupling reaction in the reaction formula (B-3), a Buchwald-Hartwigreaction using a palladium catalyst, an Ullmann reaction using copper ora copper compound, or the like can be given. With the above reactionformulas (B-1) to (B-3), a method in which a dibenzothiophene derivativeor a dibenzofuran derivative is coupled by one equivalent is described.However, when the compounds 2 and 7 have the same structure, twoequivalents of the dibenzothiophene derivative or dibenzofuranderivative may be coupled with the 9H-carbazole compound at the sametime.

<Synthesis Method 3>

In Synthesis Method 3, a method for synthesizing a substance in which R⁸in the above general formula (G1′) is an aryl group having 6 to 15carbon atoms or an alkyl group having 1 to 4 carbon atoms (the followinggeneral formula (G1′-3)) is described.

First, a 9H-carbazole compound in which the 2- or 3-position of9H-carbazole is substituted by an alkyl group or an aryl group and the3- or 6-position of 9H-carbazole is substituted by a halogen group (acompound 9) is coupled with a boronic acid compound of dibenzothiopheneor a boronic acid compound of dibenzofuran (a compound 2), whereby a9H-carbazole derivative (a compound 10) can be obtained (a reactionformula (C-1)).

In the reaction formula (C-1), X¹ represents oxygen or sulfur, X⁹represents a halogen group, a triflate group, or the like, X⁴ representsa boronic acid (the boronic acid may be protected by ethylene glycol orthe like), R¹ to R⁷ individually represent any one of hydrogen, an alkylgroup having 1 to 4 carbon atoms, and an aryl group having 6 to 15carbon atoms, and R¹⁶ represents any of an alkyl group having 1 to 4carbon atoms and an aryl group having 6 to 15 carbon atoms. As thecoupling reaction in the reaction formula (C-1), a Suzuki-Miyauracoupling reaction using a palladium catalyst or the like can be given.

Next, the 9H-carbazole derivative (the compound 10) is coupled with ahalogenated aryl (a compound 4), whereby a compound (G1′-3), which isthe object of the synthesis, can be obtained (a reaction formula (C-2)).

In the reaction formula (C-2), X¹ represents oxygen or sulfur, X⁵represents a halogen group, R¹ to R⁷ individually represent any one ofhydrogen, an alkyl group having 1 to 4 carbon atoms, and an aryl grouphaving 6 to 15 carbon atoms, R¹⁶ represents any of an alkyl group having1 to 4 carbon atoms and an aryl group having 6 to 15 carbon atoms, andAr represents an aryl group that has 14 to 70 carbon atoms and includesa condensed tricyclic ring, a condensed tetracyclic ring, a condensedpentacyclic ring, a condensed hexacyclic ring, or a condensedheptacyclic ring.

Here, in the above Synthesis Methods, the compounds 3, 8, and 10 areeach a synthetic intermediate of a carbazole derivative described inEmbodiment 1. That is, a carbazole derivative represented by thefollowing general formula (G5) is a synthetic intermediate of thecarbazole derivative represented by the general formula (G1).

(In the formula, R⁰ represents a group represented by the followinggeneral formula (g1), and R⁸ represents any one of hydrogen, an alkylgroup having 1 to 4 carbon atoms, an aryl group having 6 to 15 carbonatoms, and a group represented by the following general formula (g2).Note that the substitution site of R⁰ is a carbon atom represented byeither α or β, and the substitution site of R⁸ is a carbon atomrepresented by either γ or δ.)

(In the formula, X¹ represents oxygen or sulfur, and R¹ to R⁷individually represent any one of hydrogen, an alkyl group having 1 to 4carbon atoms, and an aryl group having 6 to 15 carbon atoms.)

(In the formula, X² represents oxygen or sulfur, and R⁹ to R¹⁵individually represent any one of hydrogen, an aryl group having 6 to 15carbon atoms, and an alkyl group having 1 to 4 carbon atoms.)

Here, in a carbazole derivative represented by the general formula (G0)or (G1), in the case where the group represented by the above generalformula (g1) further includes a substituent, the substitution site ofthe substituent is preferably a site represented by R¹, R³, or R⁶ for areduction in cost of synthesizing the material owing to availability ofthe material and easiness of the synthesis. From the same point of view,it is further preferable that R¹ to R⁷ be all hydrogen. Therefore, alsoin a carbazole derivative represented by the general formula (G5), whichis a synthetic intermediate of the carbazole derivative represented bythe general formula (G0) or (G1), in the case where the grouprepresented by the above general formula (g1) further includes asubstituent, the substitution site of the substituent is preferably asite represented by R¹, R³, or R⁶, and it is further preferable that R¹to R⁷ be all hydrogen.

In a similar manner, in the case where the group represented by (g2) isapplied as R⁸, the substitution site of the substituent is preferably asite represented by R⁹, R¹¹, or R¹⁴, and it is further preferable thatR⁹ to R¹⁵ be all hydrogen.

Note that the compound 3 having a preferred structure in which R¹ to R⁷are all hydrogen is a carbazole derivative represented by the followinggeneral formula (G6).

Note that the compound 8 having a preferred structure in which R¹ to R⁷and R⁹ to R¹⁵ are all hydrogen is any of carbazole derivativesrepresented by the following general formulas (G7) and (G8).

As specific examples of an alkyl group having 1 to 4 carbon atoms and anaryl group having 6 to 15 carbon atoms, which can be applied to any ofR¹ to R¹⁵ in the carbazole derivative represented by the above generalformula (G5), groups represented by the structural formulas (R-1) to(R-23), which are described in Embodiment 1 as groups applicable to anyof R¹ to R¹⁵ in the general formula (G0) or (G1), can be applied.

Specific examples of the carbazole derivative represented by the abovegeneral formula (G5) are shown by the following structural formulas(UT-1) to (UT61), (UT-63) to (UT-137), and (UF-1) to (UF-137).

(Embodiment 3)

This embodiment shows an example in which any of the carbazolederivatives described in Embodiment 1 is used for an active layer of avertical transistor (SIT), which is a kind of an organic semiconductorelement.

The element has a structure in which a thin-film active layer 1202containing the carbazole derivative described in Embodiment 1 isinterposed between a source electrode 1201 and a drain electrode 1203,and a gate electrode 1204 is embedded in the active layer 1202, asillustrated in FIG. 2. The gate electrode 1204 is electrically connectedto a unit to apply a gate voltage, and the source electrode 1201 and thedrain electrode 1203 are electrically connected to a unit to control avoltage between the source and the drain.

In such an element structure, when a voltage is applied between thesource and the drain under the condition where a gate voltage is notapplied, a current flows (an ON state). Then, when a gate voltage isapplied in this state, a depletion layer is generated in the peripheryof the gate electrode 1204, and thus a current does not flow (an OFFstate). With such a mechanism, the element operates as a transistor.

In a vertical transistor, a material which has both a carrier-transportproperty and favorable film quality is required for an active layer likein a light-emitting element. The carbazole derivative described inEmbodiment 1 can be suitably used because it sufficiently meets theserequirements.

(Embodiment 4)

In this embodiment, one embodiment of a light-emitting element using anyof the carbazole derivatives described in Embodiment 1 is described withreference to FIG. 1A.

A light-emitting element of this embodiment includes a plurality oflayers between a pair of electrodes. In this embodiment, thelight-emitting element includes a first electrode 102, a secondelectrode 104, and a layer 103 containing an organic compound providedbetween the first electrode 102 and the second electrode 104. Inaddition, in this embodiment, the first electrode 102 functions as ananode and the second electrode 104 functions as a cathode. In otherwords, when a voltage is applied between the first electrode 102 and thesecond electrode 104 such that the potential of the first electrode 102is higher than that of the second electrode 104, light emission can beobtained.

The substrate 101 is used as a support of the light-emitting element. Asthe substrate 101, glass, plastic or the like can be used, for example.Note that a material other than glass or plastic can be used as long asit can function as a support of a light-emitting element.

The first electrode 102 is preferably formed using a metal, an alloy, aconductive compound, a mixture of them, or the like having a high workfunction (specifically, a work function of 4.0 eV or higher).Specifically, for example, indium oxide-tin oxide (ITO: indium tinoxide), indium oxide-tin oxide containing silicon or silicon oxide,indium oxide-zinc oxide (IZO: indium zinc oxide), indium oxidecontaining tungsten oxide and zinc oxide (IWZO), and the like can begiven. Films of these conductive metal oxides are usually formed bysputtering; however, a sol-gel method or the like may also be used. Forexample, indium oxide-zinc oxide (IZO) can be formed by a sputteringmethod using a target in which zinc oxide is added to indium oxide at 1wt % to 20 wt %. Moreover, indium oxide containing tungsten oxide andzinc oxide (IWZO) can be formed by a sputtering method using a target inwhich tungsten oxide is added to indium oxide at 0.5 wt % to 5 wt % andzinc oxide is added to indium oxide at 0.1 wt % to 1 wt %. Besides, gold(Au), platinum (Pt), nickel (Ni), tungsten (W), chromium (Cr),molybdenum (Mo), iron (Fe), cobalt (Co), copper (Cu), palladium (Pd),graphene, nitride of a metal material (e.g., titanium nitride), and thelike can be given.

There is no particular limitation on a stacked structure of the layer103 containing an organic compound. The layer 103 containing an organiccompound may be formed as appropriate by combining a layer that containsa substance having a high electron-transport property, a layer thatcontains a substance having a high hole-transport property, a layer thatcontains a substance having a high electron-injection property, a layerthat contains a substance having a high hole-injection property, a layerthat contains a bipolar substance (a substance having a high electron-and hole-transport property), and the like. For example, the layer 103containing an organic compound can be formed as appropriate by combininga hole-injection layer, a hole-transport layer, a light-emitting layer,an electron-transport layer, an electron-injection layer, and the like.In this embodiment, described is a structure in which the layer 103containing an organic compound includes a hole-injection layer 111, ahole-transport layer 112, a light-emitting layer 113, and anelectron-transport layer 114 stacked in that order over the firstelectrode 102. Specific materials to form each of the layers are givenbelow.

The hole-injection layer 111 contains a substance having a highhole-injection property. Molybdenum oxide, vanadium oxide, rutheniumoxide, tungsten oxide, manganese oxide, or the like can be used.Alternatively, the hole-injection layer 111 can be formed using aphthalocyanine-based compound such as phthalocyanine (abbreviation:H₂Pc) or copper phthalocyanine (abbreviation: CuPc), an aromatic aminecompound such as4,4′-bis[N-(4-diphenylaminophenyl)-N-phenylamino]biphenyl (abbreviation:DPAB) or N,N′-bis[4-[bis(3-methylphenyl)amino]phenyl]-N,N′-diphenyl-[1,1′-biphenyl]-4,4′-diamine(abbreviation: DNTPD), a high molecular compound such aspoly(ethylenedioxythiophene)/poly(styrenesulfonic acid) (PEDOT/PSS), orthe like.

Alternatively, the hole-injection layer 111 can be formed using acomposite material in which a substance having an acceptor property ismixed into a substance having a high hole-transport property. Note that,by using such a substance having an acceptor property into which asubstance having a high hole-transport property is mixed, a materialused to form an electrode may be selected regardless of its workfunction. In other words, besides a material having a high workfunction, a material having a low work function can also be used for thefirst electrode 102. As the acceptor substance,7,7,8,8-tetracyano-2,3,5,6-tetrafluoroquinodimethane (abbreviation:F₄-TCNQ), chloranil, and the like can be given. In addition, atransition metal oxide can be given. In addition, an oxide of metalsthat belong to Group 4 to Group 8 of the periodic table can be given.Specifically, vanadium oxide, niobium oxide, tantalum oxide, chromiumoxide, molybdenum oxide, tungsten oxide, manganese oxide, and rheniumoxide are preferable because their electron-accepting property is high.Among these, molybdenum oxide is especially preferable because it isstable in the air and its hygroscopic property is low and is easilytreated.

As the substance having a high hole-transport property used for thecomposite material, any of various compounds such as an aromatic aminecompound, a carbazole derivative, aromatic hydrocarbon, and a highmolecular compound (e.g., an oligomer, a dendrimer, or a polymer) can beused. The organic compound used for the composite material is preferablyan organic compound having a high hole-transport property. Specifically,a substance having a hole mobility of 10⁻⁶ cm²/Vs or higher ispreferably used. However, another substance whose hole-transportproperty is higher than the electron-transport property may also beused. An organic compound which can be used as a substance having a highhole-transport property in the composite material is specifically givenbelow.

Examples of the aromatic amine compound includeN,N′-di(p-tolyl)-N,N′-diphenyl-p-phenylenediamine (abbreviation:DTDPPA), 4,4′-bis[N-(4-diphenylaminophenyl)-N-phenylamino]biphenyl(abbreviation: DPAB),N,N′-bis[4-[bis(3-methylphenyl)amino]phenyl]-N,N′-diphenyl-[1,1′-biphenyl]-4,4′-diamine(abbreviation: DNTPD),1,3,5-tris[N-(4-diphenylaminophenyl)-N-phenylamino]benzene(abbreviation: DPA3B), and the like.

Examples of the carbazole derivative which can be used for the compositematerial specifically include3-[N-(9-phenylcarbazol-3-yl)-N-phenylamino]-9-phenylcarbazole(abbreviation: PCzPCA1),3,6-bis[N-(9-phenylcarbazol-3-yl)-N-phenylamino]-9-phenylcarbazole(abbreviation: PCzPCA2),3-[N-(1-naphthyl)-N-(9-phenylcarbazol-3-yl)amino]-9-phenylcarbazole(abbreviation: PCzPCN1), and the like.

Examples of the carbazole derivative which can be used for the compositematerial also include 4,4′-di(N-carbazolyl)biphenyl (abbreviation: CBP),1,3,5-tris[4-(N-carbazolyl)phenyl]benzene (abbreviation: TCPB),9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole (abbreviation: CzPA),1,4-bis[4-(N-carbazolyl)phenyl]-2,3,5,6-tetraphenylbenzene, and thelike.

Examples of the aromatic hydrocarbon which can be used for the compositematerial include 2-tert-butyl-9,10-di(2-naphthyl)anthracene(abbreviation: t-BuDNA), 2-tert-butyl-9,10-di(1-naphthyl)anthracene,9,10-bis(3,5-diphenylphenyl)anthracene (abbreviation: DPPA),2-tert-butyl-9,10-bis(4-phenylphenyl)anthracene (abbreviation: t-BuDBA),9,10-di(2-naphthyl) anthracene (abbreviation: DNA),9,10-diphenylanthracene (abbreviation: DPAnth), 2-tert-butylanthracene(abbreviation: t-BuAnth), 9,10-bis(4-methyl-1-naphthyl)anthracene(abbreviation: DMNA),2-tert-butyl-9,10-bis[2-(1-naphthyl)phenyl]anthracene,9,10-bis[2-(1-naphthyl)phenyl]anthracene,2,3,6,7-tetramethyl-9,10-di(1-naphthyl) anthracene,2,3,6,7-tetramethyl-9,10-di(2-naphthyl)anthracene, 9,9′-bianthryl,10,10′-diphenyl-9,9′-bianthryl,10,10′-bis(2-phenylphenyl)-9,9′-bianthryl,10,10′-bis[(2,3,4,5,6-pentaphenyl)phenyl]-9,9′-bianthryl, anthracene,tetracene, rubrene, perylene, and 2,5,8,11-tetra(tert-butyl)perylene.Besides, pentacene, coronene, or the like can also be used. Thus,aromatic hydrocarbon having a hole mobility of 1×10⁻⁶ cm²/Vs or higherand having 14 to 42 carbon atoms is more preferably used.

The aromatic hydrocarbon which can be used for the composite materialmay have a vinyl skeleton. Examples of the aromatic hydrocarbon having avinyl group include 4,4′-bis(2,2-diphenylvinyl)biphenyl (abbreviation:DPVBi), 9,10-bis[4-(2,2-diphenylvinyl)phenyl]anthracene (abbreviation:DPVPA), and the like.

Moreover, a high molecular compound such as poly(N-vinylcarbazole)(abbreviation: PVK), poly(4-vinyltriphenylamine) (abbreviation: PVTPA),poly[N-(4-{N′-[4-(4-diphenylamino)phenyl]phenyl-N′-phenylamino}phenyl)methacrylamide](abbreviation: PTPDMA), orpoly[N,N′-bis(4-butylphenyl)-N,N′-bis(phenyl)benzidine] (abbreviation:poly-TPD) can also be used.

Note that any of the carbazole derivatives described in Embodiment 1 canalso be used as the organic compound in the composite material. Thecarbazole derivative described in Embodiment 1 is preferably containedin the hole-transport layer of the light-emitting element of thisembodiment because in this case injection of holes from thehole-injection layer to the hole-transport layer can be smoothlyperformed, and thus, the driving voltage can be reduced. For the samereason, in the case where the carbazole derivative described inEmbodiment 1 is used as an organic compound in the composite material,it is more preferable that the carbazole derivative and the carbazolederivative used for the hole-transport layer be the same substance.

The hole-transport layer 112 contains a substance having a highhole-transport property. In this embodiment, the carbazole derivativedescribed in Embodiment 1 is used for the hole-transport layer.

The light-emitting layer 113 contains a light-emitting substance. Thelight-emitting layer 113 may be formed using a film containing only alight-emitting substance or a film in which an emission center substanceis dispersed in a host material.

There is no particular limitation on a material that can be used as thelight-emitting substance or the emission center substance in thelight-emitting layer 113, and light emitted from the material may beeither fluorescence or phosphorescence. Examples of the light-emittingsubstance or the emission center substance include the following.Examples of a fluorescent substance includeN,N′-bis[4-(9H-carbazol-9-yl)phenyl]-N,N′-diphenylstilbene-4,4′-diamine(abbreviation: YGA2S),4-(9H-carbazol-9-yl)-4′-(10-phenyl-9-anthryl)triphenylamine(abbreviation: YGAPA),4-(9H-carbazol-9-yl)-4′-(9,10-diphenyl-2-anthryl)triphenylamine(abbreviation: 2YGAPPA),N,9-diphenyl-N-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazol-3-amine(abbreviation: PCAPA), perylene, 2,5,8,11-tetra-tert-butylperylene(abbreviation: TBP),4-(10-phenyl-9-anthryl)-4′-(9-phenyl-9H-carbazol-3-yl)triphenylamine(abbreviation: PCBAPA),N,N″-(2-tert-butylanthracene-9,10-diyldi-4,1-phenylene)bis[N,N′,N′-triphenyl-1,4-phenylenediamine](abbreviation: DPABPA),N,9-diphenyl-N-[4-(9,10-diphenyl-2-anthryl)phenyl]-9H-carbazol-3-amine(abbreviation: 2PCAPPA),N-[4-(9,10-diphenyl-2-anthryl)phenyl]-N,N′,N-triphenyl-1,4-phenylenediamine(abbreviation: 2DPAPPA),N,N,N′,N′,N″,N″,N′″,N′″-octaphenyldibenzo[g,p]chrysene-2,7,10,15-tetraamine(abbreviation: DBC1), coumarin 30,N-(9,10-diphenyl-2-anthryl)-N,9-diphenyl-9H-carbazol-3-amine(abbreviation: 2PCAPA),N-[9,10-bis(1,1′-biphenyl-2-yl)-2-anthryl]-N,9-diphenyl-9H-carbazol-3-amine(abbreviation: 2PCABPhA),N-(9,10-diphenyl-2-anthryl)-N,N′,N′-triphenyl-1,4-phenylenediamine(abbreviation: 2DPAPA),N-[9,10-bis(1,1′-biphenyl-2-yl)-2-anthryl]-N,N′,N′-triphenyl-1,4-phenylenediamine(abbreviation: 2DPABPhA),9,10-bis(1,1′-biphenyl-2-yl)-N-[4-(9H-carbazol-9-yl)phenyl]-N-phenylanthracen-2-amine(abbreviation: 2YGABPhA), N,N,9-triphenylanthracen-9-amine(abbreviation: DPhAPhA), coumarin 545T, N,N-diphenylquinacridone(abbreviation: DPQd), rubrene,5,12-bis(1,1′-biphenyl-4-yl)-6,11-diphenyltetracene (abbreviation: BPT),2-(2-{2-[4-(dimethylamino)phenyl]ethenyl}-6-methyl-4H-pyran-4-ylidene)propanedinitrile(abbreviation: DCM1),2-{2-methyl-6-[2-(2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizin-9-yl)ethenyl]-4H-pyran-4-ylidene}propanedinitrile(abbreviation: DCM2),N,N,N′,N′-tetrakis(4-methylphenyl)tetracene-5,11-diamine (abbreviation:p-mPhTD), 7,14-diphenyl-N,N,N′,N′-tetrakis(4-methylphenyl)acenaphtho[1,2-a]fluoranthene-3,10-diamine(abbreviation: p-mPhAFD),2-{2-isopropyl-6-[2-(1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizin-9-yl)ethenyl]-4H-pyran-4-ylidene}propanedinitrile(abbreviation: DCJTI),2-{2-tert-butyl-6-[2-(1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizin-9-yl)ethenyl]-4H-pyran-4-ylidene}propanedinitrile(abbreviation: DCJTB),2-(2,6-bis{2-[4-(dimethylamino)phenyl]ethenyl}-4H-pyran-4-ylidene)propanedinitrile(abbreviation: BisDCM), and2-{2,6-bis[2-(8-methoxy-1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizin-9-yl)ethenyl]-4H-pyran-4-ylidene}propanedinitrile(abbreviation: BisDCJTM). Examples of a phosphorescent substance includebis[2-(3′,5′-bistrifluoromethylphenyl)pyridinato-N,C^(2′)]iridium(III)picolinate(abbreviation: Ir(CF₃ppy)₂(pic)),bis[2-(4′,6′-difluorophenyl)pyridinato-N,C^(2′)]iridium(III)acetylacetonate (abbreviation: FIracac),tris(2-phenylpyridinato)iridium(III)-(abbreviation: Ir(ppy)₃),bis(2-phenylpyridinato)iridium(III) acetylacetonate (abbreviation:Ir(ppy)₂(acac)), tris(acetylacetonato)(monophenanthroline)terbium(III)(abbreviation: Tb(acac)₃(Phen)) bis(benzo quinolinato)iridium(III)acetylacetonate (abbreviation: Ir(bzq)₂(acac)),bis(2,4-diphenyl-1,3-oxazolato-N,C^(2′))iridium(III) acetylacetonate(abbreviation: Ir(dpo)₂(acac)),bis[2-(4′-perfluorophenylphenyl)pyridinato]iridium(III) acetylacetonate(abbreviation: Ir(p-PF-ph)₂(acac)),bis(2-phenylbenzothiazolato-N,C^(2′))iridium(III)acetylacetonate(abbreviation: Ir(bt)₂(acac)),bis[2-(2′-benzo[4,5-a]thienyl)pyridinato-N,C^(3′)]iridium(acetylacetonate)(abbreviation: Ir(btp)₂(acac)),bis(1-phenylisoquinolinato-N,C^(2′))iridium(III)acetylacetonate(abbreviation: Ir(piq)₂(acac)),(acetylacetonato)bis[2,3-bis(4-fluorophenyl)quinoxalinato]iridium(III)(abbreviation: Ir(Fdpq)₂(acac)),(acetylacetonato)bis(2,3,5-triphenylpyrazinato)iridium(III)(abbreviation: Ir(tppr)₂(acac)),2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine platinum(II)(abbreviation: PtOEP),tris(1,3-diphenyl-1,3-propanedionato)(monophenanthroline)europium(III)(abbreviation: Eu(DBM)₃(Phen)), andtris[1-(2-thenoyl)-3,3,3-trifluoroacetonato](monophenanthroline)europium(III)(abbreviation: Eu(TTA)₃(Phen)).

There is no particular limitation on a material that can be used as theabove host material, and for example, a metal complex, a heterocycliccompound, or an aromatic amine compound can be used. Examples of themetal complex include tris(8-quinolinolato)aluminum(III) (abbreviation:Alq), tris(4-methyl-8-quinolinolato)aluminum(III) (abbreviation: Almq₃),bis(10-hydroxybenzo[h]quinolinato)beryllium(II) (abbreviation: BeBq₂),bis(2-methyl-8-quinolinolato)(4-phenylphenolato)aluminum(III)(abbreviation: BAlq), bis(8-quinolinolato)zinc(II) (abbreviation: Znq),bis[2-(2-benzoxazolyl)phenolato]zinc(II) (abbreviation: ZnPBO),bis[2-(2-benzothiazolyl)phenolato]zinc(II) (abbreviation: ZnBTZ), andthe like. Examples of the heterocyclic compounds include2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (abbreviation:PBD), 1,3-bis[5-(p-tert-butylphenyl)-1,3,4-oxadiazol-2-yl]benzene(abbreviation: OXD-7),3-(4-biphenylyl)-4-phenyl-5-(4-tert-butylphenyl)-1,2,4-triazole(abbreviation: TAZ), 2,2′,2″-(1,3,5-benzenetriyl)tris(1-phenyl-1H-benzimidazole) (abbreviation: TPBI), bathophenanthroline(abbreviation: BPhen), bathocuproine (abbreviation: BCP),9-[4-(5-phenyl-1,3,4-oxadiazol-2-yl)phenyl]-9H-carbazole (abbreviation:CO11), and the like. Examples of the aromatic amine compound include4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (abbreviation: NPB orα-NPD), N,N′-bis(3-methylphenyl)-N,N′-diphenyl-[1,1′-biphenyl]-4,4′-diamine(abbreviation: TPD),4,4′-bis[N-(Spiro-9,9′-bifluoren-2-yl)-N-phenylamino]biphenyl(abbreviation: BSPB), and the like. In addition, a condensed polycyclicaromatic compound such as an anthracene derivative, a phenanthrenederivative, a pyrene derivative, a chrysene derivative, and adibenzo[g,p]chrysene derivative can be used. Specific examples of thecondensed polycyclic aromatic compound include 9,10-diphenylanthracene(abbreviation: DPAnth),N,N-diphenyl-9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazol-3-amine(abbreviation: CzAlPA), 4-(10-phenyl-9-anthryl)triphenylamine(abbreviation: DPhPA),4-(9H-carbazol-9-yl)-4′-(10-phenyl-9-anthryl)triphenylamine(abbreviation: YGAPA),N,9-diphenyl-N-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazol-3-amine(abbreviation: PCAPA),N,9-diphenyl-N-{4-[4-(10-phenyl-9-anthryl)phenyl]phenyl}-9H-carbazol-3-amine(abbreviation: PCAPBA),N,9-diphenyl-N-(9,10-diphenyl-2-anthryl)-9H-carbazol-3-amine(abbreviation: 2PCAPA), 6,12-dimethoxy-5,11-diphenylchrysene,N,N,N′,N′,N″,N″,N′″,N′″-octaphenyldibenzo[g,p]chrysene-2,7,10,15-tetramine(abbreviation: DBC1), 9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole(abbreviation: CzPA),3,6-diphenyl-9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole(abbreviation: DPCzPA), 9,10-bis(3,5-diphenylphenyl)anthracene(abbreviation: DPPA), 9,10-di(2-naphthyl)anthracene (abbreviation: DNA),2-tert-butyl-9,10-di(2-naphthyl)anthracene (abbreviation: t-BuDNA),9,9′-bianthryl (abbreviation: BANT),9,9′-(stilbene-3,3′-diyl)diphenanthrene (abbreviation: DPNS),9,9′-(stilbene-4,4′-diyl)diphenanthrene (abbreviation: DPNS2),3,3′,3″-(benzene-1,3,5-triyl)tripyrene (abbreviation: TPB3), and thelike. One or more substances having a wider energy gap than theabove-described emission center substance may be selected from thesesubstances and known substances. Moreover, in the case where theemission center substance emits phosphorescence, a substance havinghigher triplet excitation energy (energy difference between a groundstate and a triplet excitation state) than the emission center substancemay be selected as the host material.

The light-emitting layer 113 may be a stack of two or more layers. Forexample, in the case where the light-emitting layer 113 is formed bystacking a first light-emitting layer and a second light-emitting layerin that order over the hole-transport layer, for example, the firstlight-emitting layer is formed using a substance having a hole-transportproperty as the host material and the second light-emitting layer isformed using a substance having an electron-transport property as thehost material.

In the case where the light-emitting layer having the above-describedstructure is formed using a plurality of materials, the light-emittinglayer can be formed using co-evaporation by a vacuum evaporation method;or an inkjet method, a spin coating method, a dip coating method, or thelike as a method for mixing a solution.

The electron-transport layer 114 contains a substance having a highelectron-transport property. For example, a layer containing a metalcomplex having a quinoline skeleton or a benzoquinoline skeleton, suchas tris(8-quinolinolato)aluminum (abbreviation: Alq),tris(4-methyl-8-quinolinolato)aluminum (abbreviation: Almq₃),bis(10-hydroxybenzo[h]-quinolinato)beryllium (abbreviation: BeBq₂), orbis(2-methyl-8-quinolinolato)(4-phenylphenolato)aluminum (abbreviation:BAlq), or the like can be used. Alternatively, a metal complex having anoxazole-based or thiazole-based ligand, such asbis[2-(2-hydroxyphenyl)benzoxazolato]zinc (abbreviation: Zn(BOX)₂) orbis[2-(2-hydroxyphenyl)benzothiazolato]zinc (abbreviation: Zn(BTZ)₂), orthe like can be used. Besides the metal complexes,2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (abbreviation:PBD), 1,3-bis[5-(p-tert-butylphenyl)-1,3,4-oxadiazol-2-yl]benzene(abbreviation: OXD-7),3-(4-biphenylyl)-4-phenyl-5-(4-tert-butylphenyl)-1,2,4-triazole(abbreviation: TAZ), bathophenanthroline (abbreviation: BPhen),bathocuproine (abbreviation: BCP), or the like can also be used. Thesubstances mentioned here mainly have an electron mobility of 10⁻⁶cm²/Vs or higher. However, another substance whose electron-transportproperty is higher than the hole-transport property may also be used forthe electron-transport layer.

Furthermore, the electron-transport layer is not limited to a singlelayer, and two or more layers containing the above-described substancesmay be stacked.

Further, a layer that controls transport of electron carriers may beprovided between the electron-transport layer and the light-emittinglayer. Specifically, the layer that controls transport of electroncarriers is a layer formed by adding a small amount of substance havinga high electron-trapping property to the material having a highelectron-transport property as described above, so that carrier balancecan be adjusted. Such a structure is very effective in suppressing aproblem (such as shortening of element lifetime) caused when electronspass through the light-emitting layer.

In addition, an electron-injection layer may be provided between theelectron-transport layer and the second electrode 104, in contact withthe second electrode 104. As the electron-injection layer, an alkalimetal, an alkaline earth metal, or a compound thereof such as lithiumfluoride (LiF), cesium fluoride (CsF), or calcium fluoride (CaF₂) can beused. For example, a layer that is formed using a substance having anelectron-transport property and contains an alkali metal, an alkalineearth metal, or a compound thereof, such as an Alq layer containingmagnesium (Mg), may be used. A layer that is formed using a substancehaving an electron-transport property and contains an alkali metal or analkaline earth metal is more preferably used as the electron-injectionlayer because electrons from the second electrode 104 is efficientlyinjected.

The second electrode 104 can be formed using a metal, an alloy, anelectrically conductive compound, a mixture of them, or the like havinga low work function (specifically, a work function of 3.8 eV or lower).Specific examples of such a cathode material include an elementbelonging to Group 1 or 2 in the periodic table, i.e., an alkali metalsuch as lithium (Li) or cesium (Cs), or an alkaline earth metal such asmagnesium (Mg), calcium (Ca), or strontium (Sr); an alloy containing anyof them (e.g., MgAg or AlLi); a rare earth metal such as europium (Eu)or ytterbium (Yb); an alloy containing such a rare earth metal; and thelike. However, when the electron-injection layer is provided between thesecond electrode 104 and the electron-transport layer, the secondelectrode 104 can be formed using any of a variety of conductivematerials such as Al, Ag, ITO, or indium oxide-tin oxide containingsilicon or silicon oxide regardless of its work function. Films of theseconductive materials can be formed by a sputtering method, an inkjetmethod, a spin coating method, or the like.

Further, any of a variety of methods can be employed for forming thelayer 103 containing an organic compound regardless of a dry process ora wet process. For example, a vacuum evaporation method, an inkjetmethod, a spin coating method or the like may be used. A differentformation method may be employed for each electrode or each layer.

In addition, the electrode may be formed by a wet method using a sol-gelmethod, or by a wet method using paste of a metal material.Alternatively, the electrode may be formed by a dry method such as asputtering method or a vacuum evaporation method.

In the light-emitting element having the above-described structure, acurrent flows due to a potential difference made between the firstelectrode 102 and the second electrode 104, a hole and an electron arerecombined in the light-emitting layer 113, which contains a substancehaving a high light-emitting property, and light is emitted. That is, alight-emitting region is formed in the light-emitting layer 113.

The emitted light is extracted out through one or both of the firstelectrode 102 and the second electrode 104. Therefore, one or both ofthe first electrode 102 and the second electrode 104 arelight-transmitting electrodes. In the case where only the firstelectrode 102 is a light-transmitting electrode, the emitted light isextracted from the substrate side through the first electrode 102. Inthe case where only the second electrode 104 is a light-transmittingelectrode, the emitted light is extracted from the side opposite to thesubstrate side through the second electrode 104. In a case where each ofthe first electrode 102 and the second electrode 104 is alight-transmitting electrode, the emitted light is extracted from boththe substrate side and the side opposite to the substrate through thefirst electrode 102 and the second electrode 104.

The structure of the layers provided between the first electrode 102 andthe second electrode 104 is not limited to the above-describedstructure. However, a structure in which a light-emitting region forrecombination of holes and electrons is positioned away from the firstelectrode 102 and the second electrode 104 so as to prevent quenchingdue to the proximity of the light-emitting region and a metal used forelectrodes and carrier-injection layers is preferable. The order ofstacking the layers is not limited thereto, and the following order,which is opposite to that in FIG. 1A, may be employed: the secondelectrode, the electron-injection layer, the electron-transport layer,the light-emitting layer, the hole-transport layer, the hole-injectionlayer, and the first electrode over the substrate.

In addition, as for the hole-transport layer or the electron-transportlayer in direct contact with the light-emitting layer, particularly acarrier-transport layer in contact with a side closer to alight-emitting region in the light-emitting layer 113, in order tosuppress energy transfer from an exciton which is generated in thelight-emitting layer, it is preferable that the energy gap thereof bewider than the energy gap of the light-emitting substance contained inthe light-emitting layer or the energy gap of the emission centersubstance contained in the light-emitting layer.

Since the light-emitting element of this embodiment uses the carbazolederivative described in Embodiment 1, which has a wide energy gap, forthe hole-transport layer, light emission can be obtained efficientlyeven when the light-emitting substance or the emission center substanceis a substance that has a wide energy gap and emits blue fluorescence ora substance that has high triplet excitation energy (energy differencebetween a ground state and a triplet excited state) and emits greenphosphorescence; thus, a light-emitting element with high emissionefficiency can be provided. Accordingly, a light-emitting element havinglower power consumption can be provided. In addition, a light-emittingelement that emits light with high color purity can be provided.Further, the carbazole derivative described in Embodiment 1 has anexcellent carrier-transport property; therefore, a light-emittingelement driven with a low driving voltage can be provided.

In this embodiment, the light-emitting element is formed over asubstrate formed of glass, plastic, or the like. By fabricating aplurality of such light-emitting elements over one substrate, a passivematrix light-emitting device can be fabricated. In addition, forexample, a thin film transistor (TFT) may be formed over a substrateformed of glass, plastic, or the like, and a light-emitting element maybe fabricated over an electrode electrically connected to the TFT. Inthis manner, an active matrix light-emitting device in which the TFTcontrols the drive of the light-emitting element can be fabricated. Notethat there is no particular limitation on the structure of the TFT.Either a staggered TFT or an inverted staggered TFT may be employed. Inaddition, crystallinity of a semiconductor used for the TFT is notparticularly limited either; an amorphous semiconductor or a crystallinesemiconductor may be used. In addition, a driver circuit formed over aTFT substrate may be constructed from both n-channel and p-channel TFTsor from one of n-channel and p-channel TFTs.

(Embodiment 5)

In this embodiment, a light-emitting element having a differentstructure from that described in Embodiment 4 is described.

Described is a structure in which light is emitted from an emissioncenter substance having a light-emitting property by forming alight-emitting layer 113 described in Embodiment 4 in such a manner thatthe emission center substance is dispersed into any of the carbazolederivatives described in Embodiment 1, i.e., a structure in which thecarbazole derivative described in Embodiment 1 is used as a hostmaterial of the light-emitting layer 113.

The carbazole derivative described in Embodiment 1 has a wide energy gapor high triplet excitation energy (energy difference between a groundstate and a triplet excited state), and thus can make anotherlight-emitting substance excited and emit light effectively; therefore,the carbazole derivative described in Embodiment 1 can be suitably usedas the host material and light emission that originates from thelight-emitting substance can be obtained. Thus, a light-emitting elementhaving high emission efficiency with small energy loss can be provided.In addition, a light-emitting element that can easily provide lightemission of a desired color that originates from the emission centersubstance can be provided. Accordingly, a light-emitting element capableof easily emitting light with high color purity can be provided.Further, the carbazole derivative described in Embodiment 1 has anexcellent carrier-transport property; therefore, a light-emittingelement driven with a low driving voltage can also be provided.

Here, there is no particular limitation on the emission center substancedispersed into the carbazole derivative described in Embodiment 1, andany of various materials can be used. Specifically, it is possible touse 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran(abbreviation: DCM1),4-(dicyanomethylene)-2-methyl-6-(julolidin-4-yl-vinyl)-4H-pyran(abbreviation: DCM2), N,N-dimethylquinacridone (abbreviation: DMQd),9,10-diphenylanthracene (abbreviation: DPA), 5,12-diphenyltetracene(abbreviation: DPT), coumarin 6, perylene, rubrene,N,N′-bis[4-(9-phenyl-9H-fluoren-9-yl)phenyl]-N,N′-diphenylpyrene-1,6-diamine(abbreviation: 1,6FLPAPrn), or another known fluorescent substance thatemits fluorescence. Alternatively, it is possible to usebis(2-phenylbenzothiazolato-N,C^(2′))iridium(III)acetylacetonate(abbreviation: Ir(bt)₂(acac)),tris(2-phenylquinolinato-N,C^(2′))iridium(III) (abbreviation: Ir(pq)₃),bis(2-phenylquinolinato-N,C^(2′))iridium(III)(acetylacetonate)(abbreviation: Ir(pq)₂(acac)),bis[2-(2′-benzo[4,5-α]thienyppyridinato-N,C^(3′)]iridium(III)acetylacetonate(abbreviation: Ir(btp)₂(acac)),bis(1-phenylisoquinolinato-N,C^(2′))iridium(III)acetylacetonate(abbreviation: Ir(piq)₂(acac)),(acetylacetonato)bis[2,3-bis(4-fluorophenyl)quinoxalinato]iridium(III)(abbreviation: Ir(Fdpq)₂(acac)),tris(2-phenylpyridinato-N,C^(2′))iridium(III) (abbreviation: Ir(ppy)₃),or 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine platinum(II)(abbreviation: PtOEP), or another known phosphorescent substance thatemits phosphorescence. In the case where the carbazole derivativedescribed in Embodiment 1 has a light-emitting property, the carbazolederivative can be used as the emission center substance. In that case,the carbazole derivative used as the host material is preferablydifferent from the carbazole derivative used as the emission centersubstance. Among the above-described substances or known substances, asubstance that has a narrower band gap or lower triplet excitationenergy than the carbazole derivative described in Embodiment 1, which isused as the host material, is selected as the emission center substance.

Further, another organic compound may be dispersed at the same time inthe light-emitting layer, in addition to the carbazole derivativedescribed in Embodiment 1 and the emission center substance dispersedinto the carbazole derivative. In this case, a substance that improvescarrier balance of the light-emitting layer is preferably used, such asthe above-described substances having a high electron-transportproperty.

Note that, regarding the layers other than the light-emitting layer 113,the structure described in Embodiment 4 can be applied as appropriate.Further, the hole-transport layer 112 can be formed using any of thematerials given as the substances having a high hole-transport propertywhich can be used in a composite material in Embodiment 4. Besides, thehole-transport layer 112 can be formed using a substance having a highhole-transport property such as the following aromatic amine compounds:4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (abbreviation: NPB),N,N′-bis(3-methylphenyl)-N,N′-diphenyl-[1,1′-biphenyl]-4,4′-diamine(abbreviation: TPD), 4,4′,4″-tris(N,N-diphenylamino)triphenylamine(abbreviation: TDATA),4,4′,4″-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine(abbreviation: MTDATA), or4,4′-bis[N-(spiro-9,9′-bifluoren-2-yl)-N-phenylamino]biphenyl(abbreviation: BSPB); or the like. Needless to say, the carbazolederivative described in Embodiment 1 can also be used. The substancesmentioned here mainly have a hole mobility of 10⁻⁶ cm²/Vs or higher.However, another substance whose hole-transport property is higher thanthe electron-transport property may also be used. Note that the layercontaining a substance having a high hole-transport property is notlimited to a single layer, and two or more layers containing theabove-described substances may be stacked.

Alternatively, a high molecular compound such as poly(N-vinylcarbazole)(abbreviation: PVK) or poly(4-vinyltriphenylamine) (abbreviation: PVTPA)can be used for the hole-transport layer 112.

(Embodiment 6)

In this embodiment, an embodiment of a light-emitting element with astructure in which a plurality of light-emitting units are stacked(hereinafter this type of light-emitting element is also referred to asa stacked element) is described with reference to FIG. 1B. Thislight-emitting element includes a plurality of light-emitting unitsbetween a first electrode and a second electrode. Each light-emittingunit can have a structure similar to that of a layer 103 containing anorganic compound described in Embodiment 4 or 5. That is, alight-emitting element described in Embodiment 4 or 5 includes a singlelight-emitting unit; the light-emitting element in this embodimentincludes a plurality of light-emitting units.

In FIG. 1B, a first light-emitting unit 511 and a second light-emittingunit 512 are stacked between a first electrode 501 and a secondelectrode 502, and a charge generation layer 513 is provided between thefirst light-emitting unit 511 and the second light-emitting unit 512.The first electrode 501 and the second electrode 502 correspond to afirst electrode 102 and a second electrode 104 in Embodiment 4,respectively, and electrodes similar to those described in Embodiment 4can be applied to the first electrode 501 and the second electrode 502.Further, the first light-emitting unit 511 and the second light-emittingunit 512 may have the same structure or different structures.

The charge generation layer 513 contains a composite material of anorganic compound and a metal oxide. This composite material of anorganic compound and a metal oxide is described in Embodiment 4 andcontains an organic compound and a metal oxide such as vanadium oxide,molybdenum oxide, or tungsten oxide. As the organic compound, any ofvarious compounds such as an aromatic amine compound, a carbazolederivative, aromatic hydrocarbon, and a high molecular compound (e.g.,oligomer, dendrimer, or polymer) can be used. As the organic compound,an organic compound having a hole-transport property and a hole mobilityof 10⁻⁶ cm²/Vs or higher is preferably used. However, another substancewhose hole-transport property is higher than the electron-transportproperty may also be used. The composite of an organic compound and ametal oxide has excellent carrier-injection property andcarrier-transport property, and hence, low-voltage driving andlow-current driving can be achieved.

The charge generation layer 513 may be formed by combining a layercontaining the composite material of an organic compound and metal oxidewith a layer containing another material. For example, the layercontaining the composite material of an organic compound and a metaloxide may be combined with a layer containing a compound of a substanceselected from substances having an electron-donating property and acompound having a high electron-transport property. Moreover, the layercontaining the composite material of an organic compound and a metaloxide may be combined with a transparent conductive film.

The charge generation layer 513 interposed between the firstlight-emitting unit 511 and the second light-emitting unit 512 may haveany structure as long as electrons can be injected to a light-emittingunit on one side and holes can be injected to a light-emitting unit onthe other side when a voltage is applied between the first electrode 501and the second electrode 502. For example, in FIG. 1B, any layer can beemployed as the charge generation layer 513 as long as the layer injectselectrons into the first light-emitting unit 511 and holes into thesecond light-emitting unit 512 when a voltage is applied such that thepotential of the first electrode is higher than that of the secondelectrode.

Although the light-emitting element having two light-emitting units isdescribed in this embodiment, the present invention can be similarlyapplied to a light-emitting element in which three or morelight-emitting units are stacked. A plurality of light-emitting unitswhich are partitioned by the charge generation layer are arrangedbetween a pair of electrodes, as in the light-emitting element of thisembodiment, whereby the element can emit light in a high luminanceregion while current density is kept low. Since the current density canbe kept low, the element can have a long lifetime. When thelight-emitting element is applied for illumination, voltage drop due toresistance of an electrode material can be reduced, thereby achievinghomogeneous light emission in a large area. Moreover, the light-emittingdevice can be driven with a low driving voltage and consume less power.

By making emission colors of the light-emitting units different fromeach other, light of a desired color can be obtained from thelight-emitting element as a whole. For example, in a light-emittingelement including two light-emitting units, the emission colors of thefirst light-emitting unit and the second light-emitting unit are madecomplementary, so that the light-emitting element which emits whitelight as the whole element can be obtained. Note that the word“complementary” means color relationship in which an achromatic color isobtained when colors are mixed. In other words, when light ofcomplementary colors is mixed, white light emission can be obtained. Thesame can be applied to a light-emitting element including threelight-emitting units. For example, when the first light-emitting unitemits red light, the second light-emitting unit emits green light, andthe third light-emitting unit emits blue light, white light can beemitted from the light-emitting element as a whole.

Since the light-emitting element of this embodiment contains thecarbazole derivative described in Embodiment 1, a light-emitting elementhaving high emission efficiency can be provided. In addition, alight-emitting element driven with a low driving voltage can beprovided. Further, a light-emitting element having a long lifetime canbe provided. In addition, the light-emitting unit containing thecarbazole derivative can provide light that originates from the emissioncenter substance with high color purity; therefore, it is easy to adjustthe color of light emitted from the light-emitting element as a whole.

Note that this embodiment can be combined with any of the otherembodiments as appropriate.

(Embodiment 7)

In this embodiment, a light-emitting device including a light-emittingelement containing any of the carbazole derivatives described inEmbodiment 1 is described.

In this embodiment, the light-emitting device including a light-emittingelement containing any of the carbazole derivatives described inEmbodiment 1 is described with reference to FIGS. 3A and 3B. Note thatFIG. 3A is a top view illustrating the light-emitting device and FIG. 3Bis a cross-sectional view of FIG. 3A taken along lines A-A′ and B-B′.The light-emitting device includes a driver circuit portion (source-sidedriver circuit) 601, a pixel portion 602, and a driver circuit portion(gate-side driver circuit) 603 which are illustrated with dotted lines.These units control light emission of the light-emitting element.Moreover, a reference numeral 604 denotes a sealing substrate; 605, asealing material; and 607, a space surrounded by the sealing material605.

Reference numeral 608 denotes a wiring for transmitting signals to beinputted into the source-side driver circuit portion 601 and thegate-side driver circuit portion 603 and receiving signals such as avideo signal, a clock signal, a start signal, and a reset signal from anFPC (flexible printed circuit) 609 serving as an external inputterminal. Although only the FPC is illustrated here, a printed wiringboard (PWB) may be attached to the FPC. The light-emitting device in thepresent specification includes, in its category, not only thelight-emitting device itself but also the light-emitting device providedwith the FPC or the PWB.

Next, the cross-sectional structure is described with reference to FIG.3B. Although the driving circuit portion and the pixel portion areformed on an element substrate 610, the source-side driving circuit 601that is the driving circuit portion, and one of the pixels in the pixelportion 602 are illustrated here.

In the source-side driver circuit 601, a CMOS circuit is formed in whichan n-channel TFT 623 and a p-channel TFT 624 are combined. Such a drivercircuit may be formed by using various circuits such as a CMOS circuit,a PMOS circuit, or an NMOS circuit. Although this embodiment shows adriver-integrated type where the driver circuit is formed over thesubstrate, the present invention is not limited to this, and the drivercircuit may be formed outside the substrate, not over the substrate.

The pixel portion 602 is formed with a plurality of pixels including aswitching TFT 611, a current controlling TFT 612, and a first electrode613 electrically connected to a drain of the current controlling TFT. Aninsulator 614 is formed so as to cover the end portions of the firstelectrode 613. Here, the insulator 614 is formed using a positive typephotosensitive acrylic resin film.

In order to improve the coverage, the insulator 614 is formed to have acurved surface with curvature at its upper or lower end portion. Forexample, in the case of using positive photosensitive acrylic for theinsulator 614, only the upper end portion of the insulator 614preferably has a curved surface with a radius of curvature of 0.2 μm to3 μm. As the insulator 614, either a negative type which becomesinsoluble in etchant by irradiation with light or a positive type whichbecomes soluble in etchant by irradiation with light can be used.

A layer 616 containing an organic compound and a second electrode 617are formed over the first electrode 613. As a material used for thefirst electrode 613 functioning as an anode, a material having a highwork function is preferably used. For example, a single-layer film of anITO film, an indium tin oxide film containing silicon, an indium oxidefilm containing zinc oxide at 2 wt % to 20 wt %, a titanium nitridefilm, a chromium film, a tungsten film, a Zn film, a Pt film, or thelike can be used. Alternatively, a stack of a titanium nitride film anda film containing aluminum as its main component, a stack of threelayers of a titanium nitride film, a film containing aluminum as itsmain component, and a titanium nitride film, or the like can be used.Note that when a stacked structure is employed, the first electrode 613has low resistance as a wiring, forms a favorable ohmic contact, and canfunction as an anode.

In addition, the layer 616 containing an organic compound is formed byany of a variety of methods such as an evaporation method using anevaporation mask, an inkjet method, and a spin coating method. The layer616 containing an organic compound contains the carbazole derivativedescribed in Embodiment 1. Further, the layer 616 containing an organiccompound may be formed using another material such as a low molecularcompound or a high molecular compound (the category of the highmolecular compound includes an oligomer and a dendrimer).

As a material used for the second electrode 617, which is formed overthe layer 616 containing an organic compound and functions as a cathode,a material having a low work function (e.g., Al, Mg, Li, Ca, or an alloyor compound thereof, such as MgAg, MgIn, AlLi, LiF, or CaF₂) ispreferably used. In the case where light generated in the layer 616containing an organic compound passes through the second electrode 617,the second electrode 617 is preferably formed using a stack of a thinmetal film and a transparent conductive film (ITO, indium oxidecontaining zinc oxide at 2 wt % to 20 wt %, indium tin oxide containingsilicon, zinc oxide (ZnO), or the like).

Note that the light-emitting element is formed by the first electrode613, the layer 616 containing an organic compound, and the secondelectrode 617. The light-emitting element has any of the structuresdescribed in Embodiments 4 to 6. The pixel portion, which includes aplurality of light-emitting elements, in the light-emitting device ofthis embodiment may include both the light-emitting element with any ofthe structures described in Embodiments 4 to 6 and the light-emittingelement with a structure other than those.

Further, a light-emitting element 618 is provided in the space 607surrounded by the element substrate 610, the sealing substrate 604, andthe sealing material 605 by pasting the sealing substrate 604 and theelement substrate 610 using the sealing material 605. The space 607 maybe filled with filler, and may be filled with an inert gas (such asnitrogen or argon), the sealing material 605, or the like.

An epoxy based resin is preferably used for the sealing material 605. Itis desirable that such a material do not transmit moisture or oxygen asmuch as possible. As a material for the sealing substrate 604, a plasticsubstrate formed of FRP (fiberglass-reinforced plastics), PVF (polyvinylfluoride), polyester, acrylic, or the like can be used besides a glasssubstrate or a quartz substrate.

In this manner, the light-emitting device manufactured using thelight-emitting element containing the carbazole derivative described inEmbodiment 1 can be obtained.

Since the light-emitting device in this embodiment uses thelight-emitting element containing the carbazole derivative described inEmbodiment 1, a light-emitting device having favorable characteristicscan be provided. Specifically, since the carbazole derivative describedin Embodiment 1 has a wide energy gap and high triplet excitation energyand can suppress energy transfer from a light-emitting substance, alight-emitting element having high emission efficiency can be provided;thus, a light-emitting device having less power consumption can beprovided. In addition, since a light-emitting element driven with a lowdriving voltage can be provided, a light-emitting device driven with alow driving voltage can be provided. Further, since the light-emittingelement using the carbazole derivative described in Embodiment 1 has along lifetime, a light-emitting device having high reliability can beprovided.

Although an active matrix light-emitting device is described in thisembodiment as described above, a passive matrix light-emitting devicemay be alternatively fabricated. FIGS. 4A and 4B illustrate a passivematrix light-emitting device fabricated according to the presentinvention. FIG. 4A is a perspective view of the light-emitting device,and FIG. 4B is a cross-sectional view taken along line X-Y in FIG. 4A.In FIGS. 4A and 4B, an electrode 952 and an electrode 956 are providedover a substrate 951, and a layer 955 containing an organic compound isprovided between the electrodes 952 and 956. An end portion of theelectrode 952 is covered with an insulating layer 953. A partition layer954 is provided over the insulating layer 953. The sidewalls of thepartition layer 954 are aslope such that the distance between bothsidewalls is gradually narrowed toward the surface of the substrate.That is, a cross section taken along the direction of the short side ofthe partition wall layer 954 is trapezoidal, and the lower side (a sidewhich is in the same direction as a plane direction of the insulatinglayer 953 and in contact with the insulating layer 953) is shorter thanthe upper side (a side which is in the same direction as the planedirection of the insulating layer 953 and not in contact with theinsulating layer 953). By providing the partition layer 954 in thismanner, defects of the light-emitting element due to static charge andthe like can be prevented. The passive matrix light-emitting device canalso be driven with low power consumption by including thelight-emitting element according to any of Embodiments 4 to 6 whichcontains the carbazole derivative described in Embodiment 1 and isoperated with a low driving voltage. In addition, the light-emittingdevice can be driven with low power consumption by including thelight-emitting element according to any of Embodiments 4 to 6 whichcontains the carbazole derivative described in Embodiment 1 andaccordingly has high emission efficiency. Further, the light-emittingdevice can have high reliability by including the light-emitting elementaccording to any of Embodiments 4 to 6 which contains the carbazolederivative described in Embodiment 1.

(Embodiment 8)

In this embodiment, electronic devices of one embodiment of the presentinvention, each including the light-emitting device described inEmbodiment 7, are described. The electronic devices in this embodimenteach include a light-emitting element containing any of the carbazolederivative described in Embodiment 1 and thus electronic devices eachhaving a display portion which consumes less power can be obtained. Inaddition, electronic devices driven with a low driving voltage can beprovided. Further, electronic devices having high reliability can beprovided.

As examples of the electronic devices each containing the carbazolederivative described in Embodiment 1, the following can be given:cameras such as video cameras and digital cameras, goggle type displays,navigation systems, audio replay devices (e.g., car audio systems andaudio systems), computers, game machines, portable information terminals(e.g., mobile computers, mobile phones, portable game machines, andelectronic book readers), image replay devices in which a recordingmedium is provided (specifically, devices that are capable of replayingrecording media, such as digital versatile discs (DVDs), and equippedwith a display device that can display an image), and the like. Specificexamples of these electronic devices are illustrated in FIGS. 5A to 5D.

FIG. 5A illustrates a television device which includes a housing 9101, asupport 9102, a display portion 9103, speaker portions 9104, video inputterminals 9105, and the like. In the display portion 9103 of thistelevision device, light-emitting elements similar to those described inany of Embodiments 4 to 6 are arranged in matrix. The light-emittingelements can have high emission efficiency because each light-emittingelement contains the carbazole derivative described in Embodiment 1. Inaddition, a light-emitting element driven with a low driving voltage canbe provided. Further, a light-emitting element having high reliabilitycan be provided. Therefore, this television device having the displayportion 9103 which is formed using the light-emitting elements consumesless power. In addition, a television device driven with a low drivingvoltage can be provided. Further, a television device having highreliability can be provided.

FIG. 5B illustrates a computer according to one embodiment of thepresent invention. The computer includes a main body 9201, a housing9202, a display portion 9203, a keyboard 9204, an external connectionport 9205, a pointing device 9206, and the like. In the display portion9203 of this computer, light-emitting elements similar to thosedescribed in any of Embodiments 4 to 6 are arranged in matrix. Thelight-emitting elements can have high emission efficiency because eachlight-emitting element contains the carbazole derivative described inEmbodiment 1. In addition, a light-emitting element driven with a lowdriving voltage can be provided. Further, a light-emitting elementhaving high reliability can be provided. Therefore, this computer havingthe display portion 9203 which is formed using the light-emittingelements consumes less power. In addition, a computer driven with a lowdriving voltage can be provided. Further, a computer having highreliability can be provided.

FIG. 5C illustrates a mobile phone according to one embodiment of thepresent invention. The mobile phone includes a main body 9401, a housing9402, a display portion 9403, an audio input portion 9404, an audiooutput portion 9405, operation keys 9406, an external connection port9407, an antenna 9408, and the like. In the display portion 9403 of thismobile phone, light-emitting elements similar to those described in anyof Embodiments 4 to 6 are arranged in matrix. The light-emittingelements can have high emission efficiency because each light-emittingelement contains the carbazole derivative described in Embodiment 1. Inaddition, a light-emitting element driven with a low driving voltage canbe provided. Further, a light-emitting element having high reliabilitycan be provided. Therefore, this mobile phone having the display portion9403 which is formed using the light-emitting elements consumes lesspower. In addition, a mobile phone driven with a low driving voltage canbe provided. Further, a mobile phone having high reliability can beprovided.

FIG. 5D illustrates a camera according to one embodiment of the presentinvention which includes a main body 9501, a display portion 9502, ahousing 9503, an external connection port 9504, a remote controlreceiving portion 9505, an image receiving portion 9506, a battery 9507,an audio input portion 9508, operation keys 9509, an eye piece portion9510, and the like. In the display portion 9502 of this camera,light-emitting elements similar to those described in any of Embodiments4 to 6 are arranged in matrix. The light-emitting elements can have highemission efficiency because each light-emitting element contains thecarbazole derivative described in Embodiment 1. In addition, alight-emitting element driven with a low driving voltage can beprovided. Further, a light-emitting element having high reliability canbe provided. Therefore, this camera having the display portion 9502which is formed using the light-emitting elements consumes less power.In addition, a camera driven with a low driving voltage can be provided.Further, a camera having high reliability can be provided.

As described above, the application range of the light-emitting devicedescribed in Embodiment 7 is so wide that the light-emitting device canbe applied to electronic devices of every field. An electronic devicewhich consumes less power can be obtained by using the carbazolederivative described in Embodiment 1. In addition, an electronic devicehaving a display portion capable of providing high-quality display withexcellent color reproducibility can be obtained.

The light-emitting device described in Embodiment 7 can also be used asa lighting device. One embodiment in which the light-emitting devicedescribed in Embodiment 7 is used as a lighting device is described withreference to FIG. 6.

FIG. 6 illustrates an example of a liquid crystal display device usingthe light-emitting device described in Embodiment 7 as a backlight. Theliquid crystal display device illustrated in FIG. 6 includes a housing901, a liquid crystal layer 902, a backlight 903, and a housing 904. Theliquid crystal layer 902 is connected to a driver IC 905. Thelight-emitting device described in Embodiment 7 is used as the backlight903, to which a current is supplied through a terminal 906.

With the use of the light-emitting device described in Embodiment 7 asthe backlight of the liquid crystal display device, a backlight havingless power consumption can be provided. Further, the light-emittingdevice described in Embodiment 7 is a lighting device with plane lightemission and can have a large area. Therefore, the backlight can have alarge area, and a liquid crystal display device having a large area canbe obtained. Furthermore, since the light-emitting device described inEmbodiment 7 is thin, it becomes possible to reduce the thickness of adisplay device.

FIG. 7 illustrates an example in which the light-emitting devicedescribed in Embodiment 7 is used as a table lamp which is a lightingdevice. The table lamp illustrated in FIG. 7 includes a housing 2001 anda light source 2002, and the light-emitting device described inEmbodiment 7 is used as the light source 2002.

FIG. 8 illustrates an example in which the light-emitting devicedescribed in Embodiment 7 is used as an indoor lighting device 3001.Since the light-emitting device described in Embodiment 7 consumes lesspower, a lighting device that consumes less power can be obtained.Further, since the light-emitting device described in Embodiment 7 canhave a large area, the light-emitting device can be used as a large-arealighting device. Further, since the light-emitting device described inEmbodiment 7 is thin, the light-emitting device can be used for alighting device having reduced thickness.

Example 1 Synthesis Example 1

In this example is described a method of synthesizing3-(dibenzothiophen-4-yl)-9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole(abbreviation: DBTCzPA-II), which is the carbazole derivativerepresented by the structural formula (358) in Embodiment 1. A structureof DBTCzPA-II is illustrated in the following structural formula.

First, a method of synthesizing 3-(dibenzothiophen-4-yl)-9H-carbazole(abbreviation: DBTCz-II), which is a synthetic intermediate ofDBTCzPA-II, is described. DBTCz-II is a carbazole derivative representedby the following structural formula. A structure of DBTCz-II isillustrated in the following structural formula.

Step 1: Synthesis of 3-(Dibenzothiophen-4-yl)-9H-carbazole(abbreviation: DBTCz-II

In a 200-mL three-neck flask were put 3.0 g (12 mmol) of3-bromocarbazole, 2.8 g (12 mmol) of dibenzothiophene-4-boronic acid,and 150 mg (0.5 mol) of tri(ortho-tolyl)phosphine, and the air in theflask was replaced with nitrogen. To this mixture were added 40 mL oftoluene, 40 mL of ethanol, and 15 mL (2.0 mol/L) of an aqueous potassiumcarbonate solution. In the flask, the mixture was degassed by beingstirred under reduced pressure. After the degassing, replacement withnitrogen was performed, and 23 mg (0.10 mmol) of palladium(II) acetatewas added to this mixture, and then the mixture was refluxed at 110° C.for 3 hours. After the reflux, the mixture was cooled to roomtemperature, and then the precipitated solid was collected by suctionfiltration. The collected solid was dissolved in 100 mL of toluene, andthis solution was filtered through Celite (produced by Wako PureChemical Industries, Ltd., Catalog No. 531-16855), Florisil (produced byWako Pure Chemical Industries, Ltd., Catalog No. 540-00135), andalumina. The solid obtained by concentration of the obtained filtratewas recrystallized from toluene/hexane, so that 1.4 g of a white solid,which was the object of the synthesis, was obtained in 32% yield. Thesynthesis scheme of Step 1 is illustrated in (a-1).

This compound was identified as 3-(dibenzothiophen-4-yl)-9H-carbazole(abbreviation: DBTCz-II) by nuclear magnetic resonance (NMR)spectroscopy. ¹H NMR data of the obtained compound are shown below. Inaddition, ¹H NMR charts are shown in FIGS. 9A and 9B.

¹H NMR (DMSO, 300 MHz):δ=7.18-7.23 (m, 1H), 7.41-7.46 (m, 1H), 7.51-7.53(m, 3H), 7.64-7.70 (m, 3H), 7.78 (dd, J₁=1.8 Hz, J₂=8.1 Hz, 1H),8.00-8.05 (m, 1H), 8.21 (d, J₁=7.8 Hz, 1H), 8.35-8.46 (m, 2H), 8.50 (d,J₁=1.8 Hz, 1H), 11.46 (s, 1H)

Step 2: Synthesis of DBTCzPA-II

To a 100-mL three-neck flask were added 1.8 g (4.4 mmol) of9-(4-bromophenyl)-10-phenylanthracene, 1.5 g (4.4 mmol) of3-(dibenzothiophen-4-yl)-9H-carbazole, and 0.85 g (8.8 mmol) of sodiumtert-butoxide. After the air in the flask was replaced with nitrogen, tothis mixture were added 25 mL of toluene and 2.2 mL oftri-(tert-butyl)phosphine (a 10 wt % hexane solution). This mixture wasdegassed by being stirred while the pressure was reduced. After thedegassing, 0.12 g (0.22 mmol) of bis(dibenzylideneacetone)palladium(0)was added to the mixture. This mixture was stirred at 110° C. for 18hours under a nitrogen stream, so that a solid was precipitated. Afterthe stirring, this mixture was cooled to room temperature, and theprecipitated solid was collected by suction filtration. The collectedsolid was dissolved in about 60 mL of toluene, and the obtained solutionwas suction-filtered through Celite (produced by Wako Pure ChemicalIndustries, Ltd., Catalog No. 531-16855), Florisil (produced by WakoPure Chemical Industries, Ltd., Catalog No. 540-00135), and alumina. Theobtained filtrate was concentrated to give a solid and the solid wasrecrystallized from toluene, so that 1.1 g of a white powder wasobtained in 36% yield. The synthesis scheme of Step 2 is illustrated in(b-1).

Then, 1.1 g of the obtained white powder was purified. Using a trainsublimation method, the purification was conducted by heating of thewhite powder at 300° C. under a pressure of 3.0 Pa with a flow rate ofargon gas of 4.0 mL/min After the purification, 1.0 g of a pale yellowsolid was obtained in 90% yield.

The pale yellow solid after the above purification was subjected tonuclear magnetic resonance (NMR) spectroscopy. The measurement data areshown below.

¹H NMR (CDCl₃, 300 MHz): δ=7.36-7.68 (m, 15H), 7.72-7.93 (m, 12H),8.19-8.286 (m, 3H), 8.57 (sd, J₁=1.5 Hz, 1H)

Further, a ¹H NMR chart is shown in FIG. 10. The measurement resultsshowed that DBTCzPA-II, which is the carbazole derivative represented bythe above structural formula, was obtained.

Next, an absorption and emission spectra of DBTCzPA-II in a toluenesolution of DBTCzPA-II are shown in FIG. 11A, and an absorption andemission spectra of a thin film of DBTCzPA-II are shown in FIG. 11B. Anultraviolet-visible spectrophotometer (V-550, manufactured by JASCOCorporation) was used for the measurements of the absorption spectra. Inthe case of the toluene solution, the measurements were made with thetoluene solution of DBTCzPA-II put in a quartz cell, and the absorptionspectrum obtained by subtraction of absorption spectra of the quartzcell and toluene from the measured spectrum is shown in the drawing. Inaddition, as for the absorption spectrum of the thin film, a sample wasprepared by evaporation of DBTCzPA-II on a quartz substrate, and theabsorption spectrum obtained by subtraction of an absorption spectrum ofquartz from the absorption spectrum of this sample is shown in thedrawing. As in the measurements of the absorption spectra, anultraviolet-visible spectrophotometer (V-550, manufactured by JASCOCorporation) was used for the measurements of the emission spectra. Theemission spectrum of the toluene solution was measured with the toluenesolution of DBTCzPA-II put in a quartz cell, and the emission spectrumof the thin film was measured with a sample prepared by evaporation ofDBTCzPA-II on a quartz substrate. Thus, it was found that the greatestemission wavelength of DBTCzPA-II in the toluene solution of DBTCzPA-IIwas around 436 nm (at an excitation wavelength of 376 nm), and that thegreatest emission wavelength of the thin film of DBTCzPA-II was around447 nm (at an excitation wavelength of 400 nm).

Further, the ionization potential of DBTCzPA-II in a thin film state wasmeasured by a photoelectron spectrometer (AC-2, manufactured by RikenKeiki, Co., Ltd.) in air. The obtained value of the ionization potentialwas converted to a negative value, so that the HOMO level of DBTCzPA-IIwas −5.73 eV. From the data of the absorption spectra of the thin filmin FIG. 11B, the absorption edge of DBTCzPA-II, which was obtained fromTauc plot with an assumption of direct transition, was 2.92 eV.Therefore, the optical energy gap of DBTCzPA-II in the solid state wasestimated at 2.92 eV; from the values of the HOMO level obtained aboveand this energy gap, the LUMO level of DBTCzPA-II was able to beestimated at −2.81 eV. It was thus found that DBTCzPA-II had a wideenergy gap of 2.92 eV in the solid state.

Further, the oxidation reaction characteristics of DBTCzPA-II weremeasured. The oxidation reaction characteristics were examined by cyclicvoltammetry (CV) measurements. Note that an electrochemical analyzer(ALS model 600A or 600C, manufactured by BAS Inc.) was used for themeasurements.

For a solution for the CV measurements, dehydrated N,N-dimethylformamide(DMF, product of Sigma-Aldrich Inc., 99.8%, catalog No. 22705-6) wasused as a solvent, and tetra-n-butylammonium perchlorate (n-Bu₄NClO₄,product of Tokyo Chemical Industry Co., Ltd., catalog No. T0836), whichwas a supporting electrolyte, was dissolved in the solvent such that theconcentration thereof was 100 mmol/L. Further, the object to be measuredwas also dissolved in the solvent such that the concentration thereofwas 2 mmol/L. A platinum electrode (a PTE platinum electrode, product ofBAS Inc.) was used as a working electrode; a platinum electrode (a VC-3Pt counter electrode (5 cm), product of BAS Inc.) was used as anauxiliary electrode; and an Ag/Ag⁺ electrode (an RE5 nonaqueous solventreference electrode, product of BAS Inc.) was used as a referenceelectrode. Note that the measurements were conducted at room temperature(20° C. to 25° C.). The scan rates for the CV measurements wereuniformly set to 0.1 V/s.

In the measurements, scanning in which the potential of the workingelectrode with respect to the reference electrode was changed from −0.05V to 1.10 V and then changed from 1.10 V to −0.05 V was one cycle, and100 cycles were performed.

The measurement results revealed that DBTCzPA-II showed propertieseffective against repetition of redox reactions between an oxidizedstate and a neutral state without a large variation in oxidation peakeven after the 100 cycles in the measurements.

Further, the HOMO level of DBTCzPA-II was determined also by calculationfrom the CV measurement results.

First, the potential energy of the reference electrode with respect tothe vacuum level used was found to be −4.94 eV. The oxidation peakpotential E_(pa) of DBTCzPA-II was 1.01 V. In addition, the reductionpeak potential thereof was 0.86 V. Therefore, a half-wave potential (anintermediate potential between E_(pa) and E_(pc)) can be calculated at0.94 V. This means that DBTCzPA-II is oxidized by an electric energy of0.94 [V vs. Ag/Ag⁺], and this energy corresponds to the HOMO level.Here, since the potential energy of the reference electrode, which wasused in this example, with respect to the vacuum level is −4.94 [eV] asdescribed above, the HOMO level of DBTCzPA-II was calculated as follows:−4.94−0.94=−5.88 [eV].

Note that the potential energy of the reference electrode (Ag/Ag⁺electrode) with respect to the vacuum level corresponds to the Fermilevel of the Ag/Ag⁺ electrode, and should be calculated from a valueobtained by measuring a substance whose potential energy with respect tothe vacuum level is known, with the use of the reference electrode(Ag/Ag⁺ electrode).

How the potential energy (eV) of the reference electrode (Ag/Ag⁺electrode), which was used in this example, with respect to the vacuumlevel is determined by calculation is specifically described. It isknown that the oxidation-reduction potential of ferrocene in methanol is+0.610 [V vs. SHE] with respect to a standard hydrogen electrode(Reference: Christian R. Goldsmith et al., J. Am. Chem. Soc., Vol. 124,No. 1, pp. 83-96, 2002). In contrast, using the reference electrode usedin this example, the oxidation-reduction potential of ferrocene inmethanol was calculated at +0.11 [V vs. Ag/Ag⁺]. Thus, it was found thatthe potential energy of the reference electrode used in this example waslower than that of the standard hydrogen electrode by 0.50 [eV].

Here, it is known that the potential energy of the standard hydrogenelectrode with respect to the vacuum level is −4.44 eV (Reference:Toshihiro Ohnishi and Tamami Koyama, High molecular EL material,Kyoritsu shuppan, pp. 64-67). Therefore, the potential energy of thereference electrode used in this example with respect to the vacuumlevel can be calculated at −4.44−0.50=−4.94 [eV].

Example 2 Synthesis Example 2

In this example is described a method of synthesizing3-(dibenzofuran-4-yl)-9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole(abbreviation: DBFCzPA-II), which is the carbazole derivativerepresented by the structural formula (758) in Embodiment 1. A structureof DBFCzPA-II is illustrated in the following structural formula.

First, a method of synthesizing 3-(dibenzofuran-4-yl)-9H-carbazole(abbreviation: DBFCz-II), which is a synthetic intermediate ofDBFCzPA-II, is described. 3-(Dibenzofuran-4-yl)-9H-carbazole is acarbazole derivative represented by the following structural formula.

Step 1: Synthesis of 3-(Dibenzofuran-4-yl)-9H-carbazole (abbreviation:DBFCz-II

In a 200-mL three-neck flask were put 2.0 g (8.1 mmol) of3-bromocarbazole, 1.7 g (8.1 mmol) of dibenzofuran-4-boronic acid, and150 mg (0.5 mol) of tri(ortho-tolyl)phosphine, and the air in the flaskwas replaced with nitrogen. To this mixture were added 20 mL of toluene,20 mL of ethanol, and 15 mL (0.2 mol) of an aqueous potassium carbonatesolution (2.0 mol/L). In the flask, the mixture was degassed by beingstirred under reduced pressure. Then, 23 mg (0.10 mmol) of palladium(II)acetate was added to this mixture, and then the mixture was refluxed at80° C. After the reflux, the mixture was cooled to room temperature, andthen the obtained solid was collected by suction filtration. Thecollected solid was dissolved in 100 mL of toluene, and this solutionwas filtered through Celite (produced by Wako Pure Chemical Industries,Ltd., Catalog No. 531-16855), Florisil (produced by Wako Pure ChemicalIndustries, Ltd., Catalog No. 540-00135), and alumina. The solidobtained by concentration of the obtained filtrate was recrystallizedfrom toluene/hexane, so that 2.3 g of a white solid was obtained in 85%yield. The synthesis scheme of Step 1 is illustrated in (a-2).

This compound was identified as 3-(dibenzofuran-4-yl)-9H-carbazole(abbreviation: DBFCz-II) by nuclear magnetic resonance (NMR)spectroscopy. ¹H NMR data of the obtained compound is shown below. Inaddition, ¹H NMR charts are shown in FIGS. 12A and 12B.

¹H NMR (CDCl₃, 300 MHz):δ=7.26-7.29 (m, 1H), 7.33-7.48 (m, 5H), 7.58 (d,J=8.4 Hz, 1H), 7.62 (d, J=8.4 Hz, 1H), 7.70 (dd, J₁=1.2 Hz, J₁=7.8 Hz,1H), 7.93 (dd, J₁=1.5 Hz, J₁=7.5 Hz, 1H), 7.97-8.02 (m, 2H), 8.16 (d,J=7.5 Hz, 2H), 8.58 (d, J=1.5 Hz, 1H)

Step 2: Synthesis of DBFCzPA-II

To a 50-mL three-neck flask were added 0.61 g (1.5 mmol) of9-(4-bromophenyl)-10-phenylanthracene, 0.50 g (1.5 mmol) of3-(dibenzofuran-4-yl)-9H-carbazole, and 0.29 g (3.0 mmol) of sodiumtert-butoxide. After the air in the flask was replaced with nitrogen, tothis mixture were added 8.0 mL of toluene and 0.76 mL oftri-(tert-butyl)phosphine (a 10 wt % hexane solution). This mixture wasdegassed by being stirred while the pressure was reduced. After thedegassing, 43 mg (0.075 mmol) of bis(dibenzylideneacetone)palladium(0)was added to the mixture. This mixture was stirred at 110° C. for 10hours under a nitrogen stream. After the stirring, the obtained mixturewas suction-filtered through Celite (produced by Wako Pure ChemicalIndustries, Ltd., Catalog No. 531-16855), Florisil (produced by WakoPure Chemical Industries, Ltd., Catalog No. 540-00135), and alumina. Anoily substance obtained by concentration of the obtained filtrate waspurified by silica gel column chromatography (developing solvent,hexane:toluene=5:1). The obtained solid was recrystallized fromtoluene/hexane, so that 0.63 g of a white powder was obtained in 63%yield. The synthesis scheme of Step 2 is illustrated in (b-2).

Then, 0.63 g of the obtained white powder was purified. Using a trainsublimation method, the purification was conducted by heating of thewhite powder at 300° C. under a pressure of 3.0 Pa with a flow rate ofargon gas of 4.0 mL/min. After the purification, 0.55 g of a pale yellowsolid was obtained in 87% yield.

The pale yellow solid after the above purification was subjected tonuclear magnetic resonance (NMR) spectroscopy. The measurement data areshown below.

¹H NMR (CDCl₃, 300 MHz):δ=7.30-7.66 (m, 15H), 7.71-7.79 (m, 6H),7.83-7.91 (m, 5H), 7.97 (dd, J₁=1.2 Hz, J₂=7.2 Hz, 1H), 8.04 (dd,J₁=0.90 Hz, J₂=7.8 Hz, 1H), 8.10 (dd, J₁=1.8 Hz, J₂=8.4 Hz, 1H), 8.31(d, J₁=7.5 Hz, 1H), 8.72 (sd, =0.90 Hz, 1H)

Further, a ¹H NMR chart is shown in FIG. 13. The measurement resultsshowed that DBFCzPA-II, which is the carbazole derivative represented bythe above structural formula, was obtained.

Next, an absorption and emission spectra of DBFCzPA-II in a toluenesolution of DBFCzPA-II are shown in FIG. 14A, and an absorption andemission spectra of a thin film of DBFCzPA-II are shown in FIG. 14B. Anultraviolet-visible spectrophotometer (V-550, manufactured by JASCOCorporation) was used for the measurements of the absorption spectra. Inthe case of the toluene solution, the measurements were made with thetoluene solution of DBFCzPA-II put in a quartz cell, and the absorptionspectrum obtained by subtraction of absorption spectra of the quartzcell and toluene from the measured spectrum is shown in the drawing. Inaddition, as for the absorption spectrum of the thin film, a sample wasprepared by evaporation of DBFCzPA-II on a quartz substrate, and theabsorption spectrum obtained by subtraction of an absorption spectrum ofquartz from the absorption spectrum of this sample is shown in thedrawing. As in the measurements of the absorption spectra, anultraviolet-visible spectrophotometer (V-550, manufactured by JASCOCorporation) was used for the measurements of the emission spectra. Theemission spectrum of the toluene solution was measured with the toluenesolution of DBFCzPA-II put in a quartz cell, and the emission spectrumof the thin film was measured with a sample prepared by evaporation ofDBFCzPA-II on a quartz substrate. Thus, it was found that the greatestemission wavelength of DBFCzPA-II in the toluene solution of DBFCzPA-IIwas around 435 nm (at an excitation wavelength of 376 nm), and that thegreatest emission wavelength of the thin film of DBFCzPA-II was around449 nm (at an excitation wavelength of 380 nm).

Further, the ionization potential of DBFCzPA-II in a thin film state wasmeasured by a photoelectron spectrometer (AC-2, manufactured by RikenKeiki, Co., Ltd.) in air. The obtained value of the ionization potentialwas converted to a negative value, so that the HOMO level of DBFCzPA-IIwas −5.64 eV. From the data of the absorption spectra of the thin filmin FIG. 14B, the absorption edge of DBFCzPA-II, which was obtained fromTauc plot with an assumption of direct transition, was 2.93 eV.Therefore, the optical energy gap of DBFCzPA-II in the solid state wasestimated at 2.93 eV; from the values of the HOMO level obtained aboveand this energy gap, the LUMO level of DBFCzPA-II was able to beestimated at −2.71 eV. It was thus found that DBFCzPA-II had a wideenergy gap of 2.93 eV in the solid state.

Further, the oxidation reaction characteristics of DBFCzPA-II weremeasured. The oxidation reaction characteristics were examined by cyclicvoltammetry (CV) measurements. Note that an electrochemical analyzer(ALS model 600A or 600C, manufactured by BAS Inc.) was used for themeasurements.

For a solution for the CV measurements, dehydrated N,N-dimethylformamide(DMF, product of Sigma-Aldrich Inc., 99.8%, catalog No. 22705-6) wasused as a solvent, and tetra-n-butylammonium perchlorate (n-Bu₄NClO₄,product of Tokyo Chemical Industry Co., Ltd., catalog No. T0836), whichwas a supporting electrolyte, was dissolved in the solvent such that theconcentration thereof was 100 mmol/L. Further, the object to be measuredwas also dissolved in the solvent such that the concentration thereofwas 2 mmol/L. A platinum electrode (a PTE platinum electrode, product ofBAS Inc.) was used as a working electrode; a platinum electrode (a VC-3Pt counter electrode (5 cm), product of BAS Inc.) was used as anauxiliary electrode; and an Ag/Ag⁺ electrode (an RE5 nonaqueous solventreference electrode, product of BAS Inc.) was used as a referenceelectrode. Note that the measurements were conducted at room temperature(20° C. to 25° C.). The scan rates for the CV measurements wereuniformly set to 0.1 V/s.

In the measurements, scanning in which the potential of the workingelectrode with respect to the reference electrode was changed from 0.35V to 0.95 V and then changed from 0.95 V to 0.35 V was one cycle, and100 cycles were performed.

The measurement results revealed that DBFCzPA-II showed propertieseffective against repetition of redox reactions between an oxidizedstate and a neutral state without a large variation in oxidation peakeven after the 100 cycles in the measurements.

Further, the HOMO level of DBFCzPA-II was determined also by calculationfrom the CV measurement results.

First, the potential energy of the reference electrode with respect tothe vacuum level used was found to be −4.94 eV, as determined inExample 1. The oxidation peak potential E_(pa) of DBFCzPA-II was 0.91 V.In addition, the reduction peak potential E_(pc) thereof was 0.78 V.Therefore, a half-wave potential (an intermediate potential betweenE_(pa) and E_(pc)) can be calculated at 0.85 V. This means thatDBFCzPA-II is oxidized by an electric energy of 0.85 [V vs. Ag/Ag⁺], andthis energy corresponds to the HOMO level. Here, since the potentialenergy of the reference electrode, which was used in this example, withrespect to the vacuum level is −4.94 [eV] as described above, the HOMOlevel of DBFCzPA-II was calculated as follows: −4.94−0.85=−5.79 [eV].

Example 3 Synthesis Example 3

In this example is described a method of synthesizing3-(dibenzothiophen-4-yl)-9-(triphenylen-2-yl)-9H-carbazole(abbreviation: DBTCzTp-II), which is the carbazole derivativerepresented by the structural formula (287) in Embodiment 1. A structureof DBTCzTp-II is illustrated in the following structural formula (5).

Step 1: Synthesis of 3-(Dibenzothiophen-4-yl)-9H-carbazole

This was synthesized as in Step 1 in Synthesis Example 1.

Step 2: Synthesis of DBTCzTp-II

In a 100-mL three-neck flask were put 1.0 g (2.9 mmol) of2-bromotriphenylene and 0.88 g (2.9 mmol) of3-(dibenzothiophen-4-yl)-9H-carbazole, and the air in the flask wasreplaced with nitrogen. To this mixture were added 15 mL of toluene,0.10 mL of tri(tert-butyl)phosphine (a 10 wt % hexane solution), 0.45 g(4.3 mmol) of sodium tert-butoxide. This mixture was degassed whilebeing stirred under reduced pressure. After the degassing, replacementwith nitrogen was performed, this mixture was heated to 80° C., and then14 mg (0.025 mmol) of bis(dibenzylideneacetone)palladium(0) was addedthereto. This mixture was stirred at 80° C. for 4 hours. After thestirring, 15 mg (0.025 mmol) of bis(dibenzylideneacetone)palladium(0)was added to this mixture, and then it was further stirred at 110° C.for 8 hours. After the stirring, about 30 mL of toluene was added to themixture, and then it was stirred at 80° C. The mixture was subjected tohot filtration through Celite (produced by Wako Pure ChemicalIndustries, Ltd., Catalog No. 531-16855), Florisil (produced by WakoPure Chemical Industries, Ltd., Catalog No. 540-00135), and alumina. Theobtained filtrate was concentrated to give a white solid. The obtainedsolid was purified by silica gel column chromatography (developingsolvent, hexane:ethyl acetate=9:1), and further recrystallized fromtoluene/hexane, so that 0.50 g of a white solid was obtained in 27%yield. The synthesis scheme of Step 2 is illustrated in (b-3).

By a train sublimation method, 0.50 g of the obtained white solid waspurified. In the purification, the pressure was 2.1 Pa, the flow rate ofargon gas was 5.0 mL/min, and the temperature of the heating was 310° C.After the purification, 0.40 g of a colorless transparent solid wasobtained in a yield of 78%.

The colorless and transparent solid after the purification was subjectedto nuclear magnetic resonance (NMR) spectroscopy. The measurement dataare shown below. In addition, ¹H NMR charts are shown in FIGS. 15A and15B.

¹H NMR (CDCl₃, 300 MHz):δ=7.37-7.41 (m, 2H), 7.45-7.52 (m, 3H),7.58-7.77 (m, 8H), 7.93 (dd, =2.1 Hz, J₁=8.7 Hz, 1H), 7.96 (dd, =1.5 Hz,J₁=7.8 Hz, 1H), 8.03 (dd, J₁=1.5 Hz, J₁=8.2 Hz, 2H), 8.31 (d, J=7.5 Hz,1H), 8.61 (dd, J₁=1.5 Hz, J₂=8.0 Hz, 1H), 8.72-8.77 (m, 4H), 8.91-8.94(m, 2H)

The measurement results showed that DBTCzTp-II, which is the carbazolederivative represented by the above structural formula (5), wasobtained.

Next, an absorption and emission spectra of DBTCzTp-II in a toluenesolution of DBTCzTp-II are shown in FIG. 16A, and an absorption andemission spectra of a thin film of DBTCzTp-II are shown in FIG. 16B. Anultraviolet-visible spectrophotometer (V-550, manufactured by JASCOCorporation) was used for the measurements of the absorption spectra. Inthe case of the toluene solution, the measurements were made with thetoluene solution of DBTCzTp-II put in a quartz cell, and the absorptionspectrum obtained by subtraction of absorption spectra of the quartzcell and toluene from the measured spectrum is shown in the drawing. Inaddition, as for the absorption spectrum of the thin film, a sample wasprepared by evaporation of DBTCzTp-II on a quartz substrate, and theabsorption spectrum obtained by subtraction of an absorption spectrum ofquartz from the absorption spectrum of this sample is shown in thedrawing. As in the measurements of the absorption spectra, anultraviolet-visible spectrophotometer (V-550, manufactured by JASCOCorporation) was used for the measurements of the emission spectra. Theemission spectrum of the toluene solution was measured with the toluenesolution of DBTCzTp-II put in a quartz cell, and the emission spectrumof the thin film was measured with a sample prepared by evaporation ofDBTCzTp-II on a quartz substrate. Thus, it was found that the greatestemission wavelengths of DBTCzTp-II in the toluene solution of DBTCzTp-IIwere around 363 nm and around 379 nm (at an excitation wavelength of 340nm), and that the greatest emission wavelength of the thin film ofDBTCzTp-II was around 390 nm (at an excitation wavelength of 336 nm).

Further, the ionization potential of DBTCzTp-II in a thin film state wasmeasured by a photoelectron spectrometer (AC-2, manufactured by RikenKeiki, Co., Ltd.) in air. The obtained value of the ionization potentialwas converted to a negative value, so that the HOMO level of DBTCzTp-IIwas −5.84 eV From the data of the absorption spectra of the thin film inFIG. 16B, the absorption edge of DBTCzTp-II, which was obtained fromTauc plot with an assumption of direct transition, was 3.34 eV.Therefore, the optical energy gap of DBTCzTp-II in the solid state wasestimated at 3.34 eV; from the values of the HOMO level obtained aboveand this energy gap, the LUMO level of DBTCzTp-II was able to beestimated at −2.50 eV. It was thus found that DBTCzTp-II had a wideenergy gap of 3.34 eV in the solid state.

Further, the oxidation reaction characteristics of DBTCzTp-II weremeasured. The oxidation reaction characteristics were examined by cyclicvoltammetry (CV) measurements. Note that an electrochemical analyzer(ALS model 600A or 600C, manufactured by BAS Inc.) was used for themeasurements.

For a solution for the CV measurements, dehydrated N,N-dimethylformamide(DMF, product of Sigma-Aldrich Inc., 99.8%, catalog No. 22705-6) wasused as a solvent, and tetra-n-butylammonium perchlorate (n-Bu₄NClO₄,product of Tokyo Chemical Industry Co., Ltd., catalog No. T0836), whichwas a supporting electrolyte, was dissolved in the solvent such that theconcentration thereof was 100 mmol/L. Further, the object to be measuredwas also dissolved in the solvent such that the concentration thereofwas 2 mmol/L. A platinum electrode (a PTE platinum electrode, product ofBAS Inc.) was used as a working electrode; a platinum electrode (a VC-3Pt counter electrode (5 cm), product of BAS Inc.) was used as anauxiliary electrode; and an Ag/Ag⁺ electrode (an RE5 nonaqueous solventreference electrode, product of BAS Inc.) was used as a referenceelectrode. Note that the measurements were conducted at room temperature(20° C. to 25° C.). The scan rates for the CV measurements wereuniformly set to 0.1 V/s.

In the measurements, scanning in which the potential of the workingelectrode with respect to the reference electrode was changed from −0.05V to 1.10 V and then changed from 1.10 V to −0.05 V was one cycle, and100 cycles were performed.

The measurement results revealed that DBTCzTp-II showed propertieseffective against repetition of redox reactions between an oxidizedstate and a neutral state without a large variation in oxidation peakeven after the 100 cycles in the measurements.

Further, the HOMO level of DBTCzTp-II was determined also by calculationfrom the CV measurement results.

First, the potential energy of the reference electrode with respect tothe vacuum level used was found to be −4.94 eV, as determined inExample 1. The oxidation peak potential E_(pa) of DBTCzTp-II was 1.01 V.In addition, the reduction peak potential E_(pc) thereof was 0.86 V.Therefore, a half-wave potential (an intermediate potential betweenE_(pa) and E_(pc)) can be calculated at 0.94 V. This means thatDBTCzTp-II is oxidized by an electric energy of 0.94 [V vs. Ag/Ag⁺], andthis energy corresponds to the HOMO level. Here, since the potentialenergy of the reference electrode, which was used in this example, withrespect to the vacuum level is −4.94 [eV] as described above, the HOMOlevel of DBTCzTp-II was calculated as follows: −4.94−0.94=−5.88 [eV].

Example 4 Synthesis Example 4

In this example is described a method of synthesizing3-(dibenzofuran-4-yl)-9-(triphenylen-2-yl)carbazole (abbreviation:DBFCzTp-II), which is the carbazole derivative represented by thestructural formula (687) in Embodiment 1. A structure of DBFCzTp-II isillustrated in the following structural formula (6).

Step 1: Synthesis of 3-(Dibenzofuran-4-yl)-9H-carbazole

This was synthesized as in Step 1 in Example 2.

Step 2: Synthesis of DBFCzTp-II

In a 50-mL three-neck flask were put 0.62 g (2.0 mmol) of2-bromotriphenylene and 0.67 g (2.0 mmol) of3-dibenzofuran-4-yl)-9H-carbazol, and the air in the flask was replacedwith nitrogen. To this mixture were added 15 mL of toluene, 0.10 mL oftri(tert-butyl)phosphine (a 10 wt % hexane solution), 0.48 g (4.3 mmol)of sodium tert-butoxide. This mixture was degassed while being stirredunder reduced pressure. After this mixture was heated at 80° C., 14 mg(0.025 mmol) of bis(dibenzylideneacetone)palladium(0) was added thereto.This mixture was stirred at 110° C. for 15.5 hours. After the stirring,the mixture was washed twice with about 30 mL of water, and the mixturewas separated into an organic layer and a washed aqueous layer. Then,the aqueous layer was subjected to extraction twice with about 30 mL oftoluene. The organic layer and the solution of the extract were combinedand washed once with about 100 mL of saturated brine. The obtainedorganic layer was dried over magnesium sulfate, and this mixture wassubjected to filtration through Celite (produced by Wako Pure ChemicalIndustries, Ltd., Catalog No. 531-16855), Florisil (produced by WakoPure Chemical Industries, Ltd., Catalog No. 540-00135), and alumina. Theobtained filtrate was concentrated to give a brown solid. The obtainedbrown solid was purified by silica gel column chromatography (developingsolvent, hexane:toluene=2:1), and further recrystallized fromhexane/toluene, so that 0.73 g of a white solid was obtained in 65%yield. The synthesis scheme of Step 2 is illustrated in (b-4).

By a train sublimation method, 0.73 g of the obtained white solid waspurified. In the purification, the pressure was 2.2 Pa, the flow rate ofargon gas was 5.0 mL/min, and the temperature of the heating was 310° C.After the purification, 0.59 g of a colorless transparent solid wasobtained in a yield of 81%.

The colorless and transparent solid after the purification was subjectedto nuclear magnetic resonance (NMR) spectroscopy. The measurement dataare shown below. In addition, ¹H NMR charts are shown in FIGS. 17A and17B. Note that FIG. 17B is a chart where the range of from 7.25 ppm to 9ppm in FIG. 17A is enlarged.

¹H NMR (CDCl₃, 300 MHz):δ=7.37-7.41 (m, 2H), 7.45-7.52 (m, 3H),7.58-7.77 (m, 8H), 7.93 (dd, J₁=2.1 Hz, J₁=8.7 Hz, 1H), 7.96 (dd, J₁=1.5Hz, J₁=7.8 Hz, 1H), 8.03 (dd, J₁=1.5 Hz, J₁=8.2 Hz, 2H), 8.31 (d, J=7.5Hz, 1H), 8.61 (dd, J₁=1.5 Hz, J₂=8.0 Hz, 1H), 8.72-8.77 (m, 4H),8.91-8.94 (m, 2H)

The measurement results showed that DBFCzTp-II, which is the carbazolederivative represented by the above structural formula, was obtained.

Next, an absorption and emission spectra of DBFCzTp-II in a toluenesolution of DBFCzTp-II are shown in FIG. 18A, and an absorption andemission spectra of a thin film of DBFCzTp-II are shown in FIG. 18B. Anultraviolet-visible spectrophotometer (V-550, manufactured by JASCOCorporation) was used for the measurements of the absorption spectra. Inthe case of the toluene solution, the measurements were made with thetoluene solution of DBFCzTp-II put in a quartz cell, and the absorptionspectrum obtained by subtraction of absorption spectra of the quartzcell and toluene from the measured spectrum is shown in the drawing. Inaddition, as for the absorption spectrum of the thin film, a sample wasprepared by evaporation of DBFCzTp-II on a quartz substrate, and theabsorption spectrum obtained by subtraction of an absorption spectrum ofquartz from the absorption spectrum of this sample is shown in thedrawing. As in the measurements of the absorption spectra, anultraviolet-visible spectrophotometer (V-550, manufactured by JASCOCorporation) was used for the measurements of the emission spectra. Theemission spectrum of the toluene solution was measured with the toluenesolution of DBFCzTp-II put in a quartz cell, and the emission spectrumof the thin film was measured with a sample prepared by evaporation ofDBFCzTp-II on a quartz substrate. Thus, it was found that the maximumemission wavelengths of DBFCzTp-II in the toluene solution of DBFCzTp-IIwere around 380 nm and around 395 nm (at an excitation wavelength of 340nm), and that the greatest emission wavelength of the thin film ofDBFCzTp-II was around 413 nm (at an excitation wavelength of 334 nm).

Further, the ionization potential of DBFCzTp-II in a thin film state wasmeasured by a photoelectron spectrometer (AC-2, manufactured by RikenKeiki, Co., Ltd.) in air. The obtained value of the ionization potentialwas converted to a negative value, so that the HOMO level of DBFCzTp-IIwas −5.79 eV. From the data of the absorption spectra of the thin filmin FIG. 18B, the absorption edge of DBFCzTp-II, which was obtained fromTauc plot with an assumption of direct transition, was 3.33 eV.Therefore, the optical energy gap of DBFCzTp-II in the solid state wasestimated at 3.33 eV; from the values of the HOMO level obtained aboveand this energy gap, the LUMO level of DBFCzTp-II was able to beestimated at −2.46 eV. It was thus found that DBFCzTp-II had a wideenergy gap of 3.33 eV in the solid state.

Further, the oxidation reaction characteristics of DBFCzTp-II weremeasured. The oxidation reaction characteristics were examined by cyclicvoltammetry (CV) measurements. Note that an electrochemical analyzer(ALS model 600A or 600C, manufactured by BAS Inc.) was used for themeasurements.

For a solution for the CV measurements, dehydrated N,N-dimethylformamide(DMF, product of Sigma-Aldrich Inc., 99.8%, catalog No. 22705-6) wasused as a solvent, and tetra-n-butylammonium perchlorate (n-Bu₄NClO₄,product of Tokyo Chemical Industry Co., Ltd., catalog No. T0836), whichwas a supporting electrolyte, was dissolved in the solvent such that theconcentration thereof was 100 mmol/L. Further, the object to be measuredwas also dissolved in the solvent such that the concentration thereofwas 2 mmol/L. A platinum electrode (a PTE platinum electrode, product ofBAS Inc.) was used as a working electrode; a platinum electrode (a VC-3Pt counter electrode (5 cm), product of BAS Inc.) was used as anauxiliary electrode; and an Ag/Ag⁺ electrode (an RE5 nonaqueous solventreference electrode, product of BAS Inc.) was used as a referenceelectrode. Note that the measurements were conducted at room temperature(20° C. to 25° C.). The scan rates for the CV measurements wereuniformly set to 0.1 V/s.

In the measurements, scanning in which the potential of the workingelectrode with respect to the reference electrode was changed from 0.00V to 1.10 V and then changed from 1.10 V to 0.00 V was one cycle, and100 cycles were performed.

The measurement results revealed that DBFCzTp-II showed propertieseffective against repetition of redox reactions between an oxidizedstate and a neutral state without a large variation in oxidation peakeven after the 100 cycles in the measurements.

Further, the HOMO level of DBFCzTp-II was determined also by calculationfrom the CV measurement results.

First, the potential energy of the reference electrode with respect tothe vacuum level used was found to be −4.94 eV, as determined inExample 1. The oxidation peak potential E_(pa) of DBFCzTp-II was 1.00 V.In addition, the reduction peak potential E_(pc) thereof was 0.83 V.Therefore, a half-wave potential (an intermediate potential betweenE_(pa) and E_(pc)) can be calculated at 0.92 V. This means thatDBFCzTp-II is oxidized by an electric energy of 0.92 [V vs. Ag/Ag⁺], andthis energy corresponds to the HOMO level. Here, since the potentialenergy of the reference electrode, which was used in this example, withrespect to the vacuum level is −4.94 [eV] as described above, the HOMOlevel of DBFCzTp-II was calculated as follows: −4.94−0.92=−5.86 [eV].

Example 5 Synthesis Example 5

In this example is described a method of synthesizing3-(dibenzofuran-4-yl)-N-(9,10-diphenylanthracen-2-yl)-9H-carbazole(abbreviation: 2DBFCzPA-II), which is the carbazole derivativerepresented by the structural formula (728) in Embodiment 1. A structureof 2DBFCzPA-II is illustrated in the following structural formula.

Step 1: Synthesis of 3-(Dibenzofuran-4-yl)-9H-carbazole

This was synthesized as in Step 1 in Example 2.

Step 2: Synthesis of 2DBFCzPA-II

To a 100-mL three-neck flask were added 1.00 g (3.00 mmol) of2-bromo-9,10-diphenylanthracene, 1.23 g (3.00 mmol) of3-(dibenzofuran-4-yl)-9H-carbazole, and 0.86 g (9.00 mmol) of sodiumtert-butoxide. After the air in the flask was replaced with nitrogen, tothis mixture were added 20 mL of toluene and 0.2 mL oftri-(tert-butyl)phosphine (a 10 wt % hexane solution). This mixture wasdegassed by being stirred while the pressure was reduced. After thedegassing, 86 mg (0.15 mmol) of bis(dibenzylideneacetone)palladium(0)was added to the mixture. This mixture was stirred at 110° C. for 10hours under a nitrogen stream. After the reflux, the mixture was cooledto room temperature, and then the obtained solid was collected bysuction filtration. The collected solid was dissolved in 100 mL oftoluene, and this solution was filtered through Celite (produced by WakoPure Chemical Industries, Ltd., Catalog No. 531-16855), Florisil(produced by Wako Pure Chemical Industries, Ltd., Catalog No.540-00135), and alumina. The obtained filtrate was concentrated to givean orange solid. The obtained solid was purified by silica gel columnchromatography. In the column chromatography, a solution oftoluene:hexane=1:5 was used as a developing solvent. The obtainedfraction was concentrated to give a pale yellow solid. The obtainedsolid was recrystallized from toluene/hexane, so that 1.27 g of a paleyellow solid was obtained in 64% yield. The synthesis scheme of Step 2is illustrated in (b-5).

This compound was identified as3-(dibenzofuran-4-yl)-N-(9,10-diphenylanthracen-2-yl)-9H-carbazole(abbreviation: 2DBFCz-II) by nuclear magnetic resonance (NMR)spectroscopy. ¹H NMR data of the obtained compound is shown below. Inaddition, ¹H NMR charts are shown in FIGS. 19A and 19B.

¹H NMR (CDCl₃, 300 MHz):δ=7.26-7.49 (m, 9H), 7.54-7.72 (m, 13H),7.75-7.79 (m, 2H), 7.92-7.97 (m, 4H), 8.01 (d, J=8.1 Hz, 1H), 8.21 (d,J=7.5 Hz, 1H), 8.63 (d, J=0.9 Hz, 1H)

Example 6 Synthesis Example 6

In this example is described a method of synthesizing3,6-bis(dibenzothiophen-4-yl)-9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole(abbreviation: DBT2CzPA-II), which is the carbazole derivativerepresented by the structural formula (201) in Embodiment 1. A structureof3,6-bis(dibenzothiophen-4-yl)-9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazoleis illustrated in the following structural formula.

First, a method of synthesizing 3,6-di(benzothiophen-4-yl)-9H-carbazole(abbreviation: DBT2Cz-II), which is a synthetic intermediate ofDBT2CzPA-II, is described. DBT2Cz-II is illustrated in the followingstructural formula.

Step 1: Synthesis of 3,6-(Dibenzothiophen-4-yl)-9H-carbazole

In a 200-mL three-neck flask were put 3.3 g (10 mmol) of3,6-dibromocarbazole, 4.6 g (20 mmol) of dibenzothiophene-4-boronicacid, and 156 mg (0.5 mol) of tri(ortho-tolyl)phosphine, and the air inthe flask was replaced with nitrogen. To this mixture were added 25 mLof toluene, 25 mL of ethanol, and 15 mL (2.0 mol/L) of an aqueouspotassium carbonate solution. In the flask, the mixture was degassed bybeing stirred under reduced pressure. After the degassing, replacementwith nitrogen was performed, and 22 mg (0.10 mmol) of palladium(II)acetate was added to this mixture, and then the mixture was refluxed at80° C. for 2 hours. After the reflux, since a white solid wasprecipitated, about 450 mL of toluene was added to this mixture and thewhite solid was dissolved. The obtained suspension was filtered throughCelite (produced by Wako Pure Chemical Industries, Ltd., Catalog No.531-16855), Florisil (produced by Wako Pure Chemical Industries, Ltd.,Catalog No. 540-00135), and alumina. The solid obtained by concentrationof the obtained filtrate was recrystallized from about 200 mL oftoluene, so that 2.0 g of a white solid, which was the object of thesynthesis, was obtained in 38% yield. The synthesis scheme of Step 1 isillustrated in (a-1).

This compound was identified as 3,6-di(benzothiophen-4-yl)-9H-carbazole(abbreviation: DBT2Cz-II) by nuclear magnetic resonance (NMR)spectroscopy. ¹H NMR data of the obtained compound is shown below. Inaddition, ¹H NMR charts are shown in FIGS. 20A and 20B.

¹H NMR (CDCl₃, 300 MHz):δ=7.44-7.50 (m, 4H), 7.57-7.64 (m, 6H),7.82-7.88 (m, 4H), 8.15-8.22 (m, 4H), 8.90 (d, J=0.9 Hz, 1H), 8.50 (d,J=1.2 Hz, 2H)

Step 2: Synthesis of DBTCzPA-II

To a 100-mL three-neck flask were added 0.95 g (2.32 mmol) of9-(4-bromophenyl)-10-phenylanthracene, 1.23 g (2.32 mmol) of3,6-di(benzothiophen-4-yl)-9H-carbazole, and 0.67 g (6.96 mmol) ofsodium tert-butoxide. After the air in the flask was replaced withnitrogen, to this mixture were added 20 mL of toluene and 0.1 mL oftri-tert-butyl-phosphine (a 10 wt % hexane solution). This mixture wasdegassed by being stirred while the pressure was reduced. After thedegassing, 24 g (0.11 mmol) of bis(dibenzylideneacetone)palladium(0) wasadded to the mixture. This mixture was stirred at 110° C. for 10 hoursunder a nitrogen stream. After the stirring, 100 mL of toluene was addedto the obtained mixture, and this suspension was suction-filteredthrough Celite (produced by Wako Pure Chemical Industries, Ltd., CatalogNo. 531-16855), Florisil (produced by Wako Pure Chemical Industries,Ltd., Catalog No. 540-00135), and alumina. The oily substance obtainedby concentration of the obtained filtrate was recrystallized fromtoluene, so that 0.75 g of a pale yellow solid, which was the object ofthe synthesis, was obtained in 38% yield. The synthesis scheme of Step 2is illustrated in (b-6).

This compound was identified as3,6-bis(dibenzothiophen-4-yl)-9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole(abbreviation: DBT2CzPA-II) by nuclear magnetic resonance (NMR)spectroscopy. ¹H NMR data of the obtained compound is shown below. Inaddition, ¹H NMR charts are shown in FIGS. 21A and 21B.

¹H NMR (CDCl₃, 300 MHz):δ=7.38-7.69 (m, 17H), 7.76-7.91 (m, 10H),7.95-7.99 (m, 4H), 8.18-8.24 (m, 4H), 8.63 (d, J=0.9 Hz, 1H)

Example 7 Synthesis Example 7

In this example is described a method of synthesizing3,6-di(benzofuran-4-yl)-9H-carbazole (abbreviation: DBF2Cz-II), which isthe carbazole derivative represented by the general formula (G5) inEmbodiment 2, which can be used as a synthetic intermediate of thecarbazole derivative described in Embodiment 1. A structure of DBF2Cz-IIis illustrated in the following structural formula.

In a 200-mL three-neck flask were put 3.00 g (9.23 mmol) of3,6-dibromocarbazole, 3.91 g (18.5 mmol) of dibenzothiophene-4-boronicacid, and 140 mg (0.46 mol) of tri(ortho-tolyl)phosphine, and the air inthe flask was replaced with nitrogen. To this mixture were added 35 mLof toluene, 10 mL of ethanol, and 20 mL (2.0 mol/L) of an aqueouspotassium carbonate solution. In the flask, the mixture was degassed bybeing stirred under reduced pressure. After the degassing, replacementwith nitrogen was performed, and 21 mg (92.3 mol) of palladium(II)acetate was added to this mixture, and then the mixture was refluxed at80° C. for 3 hours. After the reflux, about 200 mL of toluene was addedto this mixture and then the mixture was stirred at about 110° C. Whilethis suspension was kept hot, it was filtered through Celite (producedby Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855), Florisil(produced by Wako Pure Chemical Industries, Ltd., Catalog No.540-00135), and alumina. The solid obtained by concentration of theobtained filtrate was recrystallized from toluene, so that 1.40 g of awhite solid was obtained in 30% yield. The synthesis scheme isillustrated in (c−1).

This white solid was identified as3,6-bis(dibenzofuran-4-yl)-9H-carbazole (abbreviation: DBF2Cz-II) bynuclear magnetic resonance (NMR) spectroscopy. ¹H NMR data of theobtained compound is shown below. In addition, ¹H NMR charts are shownin FIGS. 22A and 22B.

¹H NMR (CDCl₃, 300 MHz):δ=7.37 (dt, J₁=0.9 Hz, J₂=7.2 Hz, 2H), 7.44-7.50(m, 4H), 7.64 (d, J=8.1 Hz, 4H), 7.74 (dd, J₁=0.9 Hz, J₂=7.7 Hz, 2H),7.95 (dd, 3, =0.9 Hz, J₂=7.5 Hz, 2H), 8.03 (dt, J=1.8 Hz, J₂=8.4 Hz,4H), 8.26 (br, 1H), 8.69 (d, J=2.1 Hz, 1H)

Example 8

In this example are described light-emitting elements in which3-(dibenzothiophen-4-yl)-9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole(abbreviation: DBTCzPA-II) and3-(dibenzofuran-4-yl)-9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole(abbreviation: DBFCzPA-II), which are carbazole derivatives described inEmbodiment 1, are respectively used as host materials in light-emittinglayers in which emission center substances that emit blue fluorescenceare used.

The molecular structures of organic compounds used in this example areillustrated in the following structural formulas (iv) to (vi). In theelement structure in FIG. 1A, an electron-injection layer is providedbetween an electron-transport layer 114 and a second electrode 104 wasemployed.

Fabrication of Light-Emitting Element 1 and Light-Emitting Element 2

First, a glass substrate 101 over which indium tin oxide containingsilicon (ITSO) with a thickness of 110 nm was formed as a firstelectrode 102 was prepared. A surface of the ITSO was covered with apolyimide film so that an area of 2 mm×2 mm of the surface was exposed.The electrode area was 2 mm×2 mm. As a pretreatment for forming thelight-emitting element over the substrate, the surface of the substratewas washed with water and baked at 200° C. for one hour, and then a UVozone treatment was performed for 370 seconds. After that, the substratewas transferred into a vacuum evaporation apparatus whose pressure wasreduced to about 10⁻⁴ Pa, vacuum baking at 170° C. for 30 minutes wasperformed in a heating chamber of the vacuum evaporation apparatus, andthen the substrate was cooled down for about 30 minutes.

Then, the substrate 101 was fixed on a holder provided in the vacuumevaporation apparatus such that the surface of the substrate 101provided with ITSO faced downward.

After the pressure in the vacuum evaporation apparatus was reduced to10⁻⁴ Pa, 9-[4-(9-phenylcarbazol-3-yl)]phenyl-10-phenylanthracene(abbreviation: PCzPA) represented by the above structural formula (v),and molybdenum(VI) oxide were co-evaporated with a mass ratio of PCzPAto molybdenum(VI) oxide being 2:1, whereby a hole-injection layer 111was formed. The thickness thereof was 50 nm.

Note that the co-evaporation is an evaporation method in which aplurality of different substances are concurrently vaporized from therespective different evaporation sources.

Next, PCzPA was evaporated to a thickness of 10 nm, whereby ahole-transport layer 112 was formed.

Further, in the light-emitting element 1, on the hole-transport layer112, DBTCzPA-II, which is the carbazole derivative represented by theabove structural formula in Embodiment 1, andN,N′-bis[4-(9-phenyl-9H-fluoren-9-yl)phenyl]-N,N′-diphenylpyrene-1,6-diamine(abbreviation: 1,6FLPAPrn) were evaporated to a thickness of 30 nm witha mass ratio of DBTCzPA-II to 1,6FLPAPrn being 1:0.05, whereby alight-emitting layer 113 was formed.

In the light-emitting element 2, on the hole-transport layer 112,DBFCzPA-II which is the carbazole derivative represented by the abovestructural formula, and 1,6FLPAPrn were evaporated to a thickness of 30nm with a mass ratio of DBFCzPA-II to 1,6FLPAPrn being 1:0.05, whereby alight-emitting layer 113 was formed.

Then, on the light-emitting layer 113,tris(8-quinolinolato)aluminum(III) represented by the above structuralformula (vii) was evaporated to a thickness of 10 nm, andbathophenanthroline (abbreviation: BPhen) represented by the abovestructural formula (iv) was evaporated to a thickness of 15 nm, wherebythe electron-transport layer 114 was formed. Further, lithium fluoridewas evaporated to a thickness of 1 nm on the electron-transport layer114, whereby the electron-injection layer was formed. Lastly, analuminum film was formed to a thickness of 200 nm as the secondelectrode 104 which serves as a cathode, whereby the light-emittingelements 1 and 2 were completed. Note that in the above evaporationprocess, evaporation was all performed by a resistance heating method.

Operation Characteristics of Light-Emitting Elements 1 and 2

The light-emitting elements 1 and 2 thus obtained were sealed in a glovebox under a nitrogen atmosphere without being exposed to air. Then, theoperation characteristics of these light-emitting elements weremeasured. Note that the measurements were carried out at roomtemperature (in an atmosphere kept at 25° C.).

FIG. 23 shows luminance vs. current density characteristics of thelight-emitting elements, FIG. 24 shows luminance vs. voltagecharacteristics thereof, and FIG. 25 shows current efficiency vs.luminance characteristics thereof. In FIG. 23, the vertical axisrepresents luminance (cd/m²), and the horizontal axis represents currentdensity (mA/cm²). In FIG. 24, the vertical axis represents luminance(cd/m²), and the horizontal axis represents voltage (V). In FIG. 25, thevertical axis represents current efficiency (cd/A), and the horizontalaxis represents luminance (cd/m²).

From FIG. 25, it is found that the light-emitting elements in each ofwhich the carbazole derivative described in Embodiment 1 is used as ahost material in a light-emitting layer of the light-emitting elementthat emits blue fluorescence show favorable luminance vs. emissionefficiency characteristics and high emission efficiency. This is becausethe carbazole derivatives described in Embodiment 1 have a wide energygap, and thus even a light-emitting substance that emits bluefluorescence and has a wide energy gap can be effectively excited. Inaddition, from FIG. 23, it is found that the light-emitting elements ineach of which the carbazole derivative described in Embodiment 1 is usedas a host material in a light-emitting layer of the light-emittingelement that emits blue fluorescence show favorable luminance vs.voltage characteristics and are driven with a low driving voltage. Thisindicates that the carbazole derivatives described in Embodiment 1 havean excellent carrier-transport property.

FIG. 26 shows emission spectra when a current of 1 mA was made to flowin the fabricated light-emitting elements. In FIG. 26, the vertical axisrepresents emission wavelength (nm), and the horizontal axis representsemission intensity. The emission intensity is shown as a value relativeto the maximum emission intensity assumed to be 1. From FIG. 26, it isfound that each of the light-emitting elements 1 and 2 emits blue lightwhich originates from 1,6FLPAPrn, which is the emission centersubstance.

Next, the initial luminance is set at 1000 cd/m², these elements weredriven under a condition where the current density was constant, andchanges in luminance with respect to the driving time were examined.FIG. 27 shows normalized luminance vs. time characteristics of thelight-emitting elements. From FIG. 27, it is found that each of thelight-emitting elements 1 and 2 shows favorable characteristics and hashigh reliability.

Example 9

In this example are described light-emitting elements described inEmbodiment 1 in which3-(dibenzothiophen-4-yl)-9-(triphenylen-2-yl)-9H-carbazole(abbreviation: DBTCzTp-II) and3-(dibenzofuran-4-yl)-9-(triphenylen-2-yl)carbazole (abbreviation:DBFCzTp-II), which are carbazole derivatives, are respectively used ashost materials in light-emitting layers in which emission centersubstances that emit green phosphorescence are used.

The molecular structures of organic compounds used in this example areillustrated in the following structural formulas (i), (iii), and (iv).In the element structure in FIG. 1A, an electron-injection layer isprovided between an electron-transport layer 114 and a second electrode104 was employed.

Fabrication of Light-Emitting Element 3 and Light-Emitting Element 4

First, a glass substrate 101 over which indium tin oxide containingsilicon (ITSO) with a thickness of 110 nm was formed as a firstelectrode 102 was prepared. A surface of the ITSO was covered with apolyimide film so that an area of 2 mm×2 mm of the surface was exposed.The electrode area was 2 mm×2 mm. As a pretreatment for forming thelight-emitting element over the substrate, the surface of the substratewas washed with water and baked at 200° C. for one hour, and then a UVozone treatment was performed for 370 seconds. Then, the substrate wastransferred into a vacuum evaporation apparatus whose pressure wasreduced to about 10⁻⁴ Pa, vacuum baking at 170° C. for 30 minutes wasperformed in a heating chamber of the vacuum evaporation apparatus, andthen the substrate was cooled down for about 30 minutes.

Then, the substrate 101 was fixed on a holder provided in the vacuumevaporation apparatus such that the surface of the substrate 101provided with ITSO faced downward.

After the pressure in the vacuum evaporation apparatus was reduced to10⁻⁴ Pa, 4-phenyl-4′-(9-phenylfluoren-9-yl)triphenylamine (abbreviation:BPAFLP) represented by the above structural formula (i), andmolybdenum(VI) oxide were co-evaporated with a mass ratio of BPAFLP tomolybdenum(VI) oxide being 2:1, whereby a hole-injection layer 111 wasformed. The thickness thereof was 50 nm. Note that the co-evaporation isan evaporation method in which a plurality of different substances areconcurrently vaporized from the respective different evaporationsources.

Next, BPAFLP was evaporated to a thickness of 10 nm, whereby ahole-transport layer 112 was formed.

Further, in the light-emitting element 3, on the hole-transport layer112, DBTCzTp-II, which is the carbazole derivative represented by theabove structural formula in Embodiment 1, andtris(2-phenylpyridinato-N,C^(2′))iridium(III) (abbreviation: Ir(ppy)₃)were evaporated to a thickness of 40 nm with a mass ratio of DBTCzTp-IIto It(ppy)₃ being 1:0.06, and then DBTCzTp-II was evaporated to athickness of 15 nm, whereby a light-emitting layer 113 was formed.

In the light-emitting element 4, on the hole-transport layer 112,DBFCzTp-II which is the carbazole derivative represented by the abovestructural formula, and Ir(ppy)₃ were evaporated to a thickness of 40 nmwith a mass ratio of DBFCzTp-II to Ir(ppy)₃ being 1:0.06, whereby alight-emitting layer 113 was formed.

Then, on the light-emitting layer 113, bathophenanthroline(abbreviation: BPhen) represented by the above structural formula (iv)was evaporated to a thickness of 15 nm, whereby the electron-transportlayer 114 was formed. Further, lithium fluoride was evaporated to athickness of 1 nm on the electron-transport layer 114, whereby theelectron-injection layer was formed. Lastly, an aluminum film was formedto a thickness of 200 nm as the second electrode 104 which serves as acathode, whereby the light-emitting elements 3 and 4 were completed.Note that in the above evaporation process, evaporation was allperformed by a resistance heating method.

Operation Characteristics of Light-Emitting Elements 3 and 4

The light-emitting elements 3 and 4 thus obtained were sealed in a glovebox under a nitrogen atmosphere without being exposed to air. Then, theoperation characteristics of these light-emitting elements weremeasured. Note that the measurements were carried out at roomtemperature (in an atmosphere kept at 25° C.).

FIG. 28 shows luminance vs. current density characteristics of thelight-emitting elements, FIG. 29 shows luminance vs. voltagecharacteristics thereof, and FIG. 30 shows current efficiency vs.luminance characteristics thereof. In FIG. 28, the vertical axisrepresents luminance (cd/m²), and the horizontal axis represents currentdensity (mA/cm²). In FIG. 29, the vertical axis represents luminance(cd/m²), and the horizontal axis represents voltage (V). In FIG. 30, thevertical axis represents current efficiency (cd/A), and the horizontalaxis represents luminance (cd/m²).

From FIG. 30, it is found that the light-emitting elements in each ofwhich the carbazole derivative described in Embodiment 1 is used as ahost material in a light-emitting layer of the light-emitting elementthat emits green phosphorescence show favorable luminance vs. emissionefficiency characteristics and high emission efficiency. This is becausethe carbazole derivatives described in Embodiment 1 have a wide energygap, and thus has high triplet excitation energy; as a result, even alight-emitting substance that emits green phosphorescence can beeffectively excited. In addition, from FIG. 28, it is found that thelight-emitting elements in each of which the carbazole derivativedescribed in Embodiment 1 is used as a host material in a light-emittinglayer of the light-emitting element that emits green phosphorescenceshow favorable luminance vs. voltage characteristics and are driven witha low driving voltage. This indicates that the carbazole derivativesdescribed in Embodiment 1 have an excellent carrier-transport property.

FIG. 31 shows emission spectra when a current of 1 mA was made to flowin the fabricated light-emitting elements 3 and 4. In FIG. 31, thevertical axis represents emission wavelength (nm), and the horizontalaxis represents emission intensity. The emission intensity is shown as avalue relative to the maximum emission intensity assumed to be 1. FromFIG. 31, it is found that each of the light-emitting elements 3 and 4emits green light which originates from Ir(ppy)₃, which is the emissioncenter substance.

Next, the initial luminance is set at 1000 cd/m², these elements weredriven under a condition where the current density was constant, andchanges in luminance with respect to the driving time were examined.FIG. 32 shows normalized luminance vs. time characteristics of thelight-emitting elements. From FIG. 32, it is found that each of thelight-emitting elements 3 and 4 shows favorable characteristics and hashigh reliability.

Example 10 Synthesis Example 8

In this example is described a method of synthesizing3-(dibenzothiophen-4-yl)-9-(9,10-diphenyl-2-anthryl)-9H-carbazole(abbreviation: 2DBTCzPA-II), which is the carbazole derivativerepresented by the structural formula (328) in Embodiment 1. A structureof 2DBTCzPA-II is illustrated in the following structural formula.

Step 1: Synthesis of 3-(Dibenzothiophen-4-yl)-9H-carbazole(abbreviation: DBTCz-II)

This was synthesized as in Step 1 in Example 1.

Step 2: Synthesis of3-(dibenzothiophen-4-yl)-9-(9,10-diphenyl-2-anthryl)-9H-carbazole(abbreviation: 2DBTCzPA-II)

To a 100-mL three-neck flask were added 1.4 g (3.0 mmol) of2-iodo-9,10-diphenylanthracene, 1.1 g (3.0 mmol) of3-(dibenzothiophen-4-yl)-9H-carbazole, and 0.86 g (9.0 mmol) of sodiumtert-butoxide. After the air in the flask was replaced with nitrogen, tothis mixture were added 20 mL of toluene and 0.2 mL oftri(tert-butyl)phosphine (a 10 wt % hexane solution). This mixture wasdegassed by being stirred while the pressure was reduced. After thedegassing, 86 mg (0.15 mmol) of bis(dibenzylideneacetone)palladium(0)was added to the mixture. This mixture was stirred at 110° C. for 4hours under a nitrogen stream. After the stirring, the obtained mixturewas suction-filtered through Celite (produced by Wako Pure ChemicalIndustries, Ltd., Catalog No. 531-16855), alumina, and Florisil(produced by Wako Pure Chemical Industries, Ltd., Catalog No.540-00135). The filtrate was concentrated to give a yellow solid. Theobtained solid was purified by silica gel column chromatography(developing solvent, hexane:toluene=5:1). The obtained fraction wasconcentrated to give a yellow solid. The obtained yellow solid wasrecrystallized from toluene/hexane, so that 1.5 g of a yellow solid wasobtained in 76% yield. The synthesis scheme of Step 2 is illustrated in(b-7).

By a train sublimation method, the obtained yellow solid was purified.The purification was conducted by heating of 1.5 g of the yellow solidat 300° C. under a pressure of 2.2 Pa with a flow rate of argon gas of 5mL/min. After the purification, 1.3 g of a yellow solid was obtained in87% yield.

The yellow solid after the above purification was subjected to nuclearmagnetic resonance (NMR) spectroscopy. The measurement result isdescribed below.

¹H NMR (CDCl₃, 300 MHz):δ=7.29-7.51 (m, 8H), 7.54-7.69 (m, 13H),7.74-7.79 (m, 3H), 7.81-7.86 (m, 1H), 7.94 (s, 1H), 7.96 (d, J₁=5.7 Hz,1H), 8.13-8.22 (m, 3H), 8.49 (d, J₁=1.5 Hz, 1H)

In addition, ¹H NMR charts are shown in FIGS. 33A and 33B. Themeasurement results showed that 2DBTCzPA-II, which is the carbazolederivative represented by the above structural formula, was obtained.

Next, an absorption and emission spectra of 2DBTCzPA-II in a toluenesolution of 2DBTCzPA-II are shown in FIG. 34A, and an absorption andemission spectra of a thin film of 2DBTCzPA-II are shown in FIG. 34B. Anultraviolet-visible spectrophotometer (V-550, manufactured by JASCOCorporation) was used for the measurements of the absorption spectra. Inthe case of the toluene solution, the measurements were made with thetoluene solution of 2DBTCzPA-II put in a quartz cell, and the absorptionspectrum obtained by subtraction of absorption spectra of the quartzcell and toluene from the measured spectrum is shown in the drawing. Inaddition, as for the absorption spectrum of the thin film, a sample wasprepared by evaporation of 2DBTCzPA-II on a quartz substrate, and theabsorption spectrum obtained by subtraction of an absorption spectrum ofquartz from the absorption spectrum of this sample is shown in thedrawing. As in the measurements of the absorption spectra, anultraviolet-visible spectrophotometer (V-550, manufactured by JASCOCorporation) was used for the measurements of the emission spectra. Theemission spectrum of toluene was measured with the toluene solution of2DBTCzPA-II put in a quartz cell, and the emission spectrum of the thinfilm was measured with a sample prepared by evaporation of 2DBTCzPA-IIon a quartz substrate. Thus, it was found that the absorption peakwavelengths of 2DBTCzPA-II in the toluene solution of 2DBTCzPA-II werearound 376 nm, around 341 nm, and around 288 nm, and the emission peakwavelengths thereof were around 438 nm and around 460 nm (at anexcitation wavelength of 377 nm), and that the absorption peakwavelengths of the thin film of 2DBTCzPA-II were around 423 nm, around381 nm, around 346 nm, and around 263 nm and the greatest emissionwavelength thereof was around 460 nm (at an excitation wavelength of 420nm).

Further, the ionization potential of 2DBTCzPA-II in a thin film statewas measured by a photoelectron spectrometer (AC-2, manufactured byRiken Keiki, Co., Ltd.) in air. The obtained value of the ionizationpotential was converted to a negative value, so that the HOMO level of2DBTCzPA-II was −5.59 eV. From the data of the absorption spectra of thethin film in FIG. 34B, the absorption edge of 2DBTCzPA-II, which wasobtained from Tauc plot with an assumption of direct transition, was2.75 eV. Therefore, the optical energy gap of 2DBTCzPA-II in the solidstate was estimated at 2.75 eV; from the values of the HOMO levelobtained above and this energy gap, the LUMO level of 2DBTCzPA-II wasable to be estimated at −2.84 eV. It was thus found that 2DBTCzPA-II hada wide energy gap of 2.75 eV in the solid state.

Further, the oxidation reaction characteristics of 2DBTCzPA-II weremeasured. The oxidation reaction characteristics were examined by cyclicvoltammetry (CV) measurements. Note that an electrochemical analyzer(ALS model 600A or 600C, manufactured by BAS Inc.) was used for themeasurements.

For a solution for the CV measurements, dehydrated N,N-dimethylformamide(DMF, product of Sigma-Aldrich Inc., 99.8%, catalog No. 22705-6) wasused as a solvent, and tetra-n-butylammonium perchlorate (n-Bu₄NClO₄,product of Tokyo Chemical Industry Co., Ltd., catalog No. T0836), whichwas a supporting electrolyte, was dissolved in the solvent such that theconcentration thereof was 100 mmol/L. Further, the object to be measuredwas also dissolved in the solvent such that the concentration thereofwas 2 mmol/L. A platinum electrode (a PTE platinum electrode, product ofBAS Inc.) was used as a working electrode; a platinum electrode (a VC-3Pt counter electrode (5 cm), product of BAS Inc.) was used as anauxiliary electrode; and an Ag/Ag⁺ electrode (an RE5 nonaqueous solventreference electrode, product of BAS Inc.) was used as a referenceelectrode. Note that the measurements were conducted at room temperature(20° C. to 25° C.). The scan rates for the CV measurements wereuniformly set to 0.1 V/s.

In the measurements, scanning in which the potential of the workingelectrode with respect to the reference electrode was changed from 0.37V to 0.90 V and then changed from 0.90 V to 0.36 V was one cycle, and100 cycles were performed.

The measurement results revealed that 2DBTCzPA-II showed propertieseffective against repetition of redox reactions between an oxidizedstate and a neutral state without a large variation in oxidation peakeven after the 100 cycles in the measurements.

Further, the HOMO level of 2DBTCzPA-II was determined also bycalculation from the CV measurement results.

First, the potential energy of the reference electrode with respect tothe vacuum level used was found to be −4.94 eV, as determined inExample 1. The oxidation peak potential E_(pa) of 2DBTCzPA-II was 0.87V. In addition, the reduction peak potential E_(pc) thereof was 0.74 V.Therefore, a half-wave potential (an intermediate potential betweenE_(pa) and E_(pc)) can be calculated at 0.81 V. This means that2DBTCzPA-II is oxidized by an electric energy of 0.81 [V vs. Ag/Ag¹],and this energy corresponds to the HOMO level. Here, since the potentialenergy of the reference electrode, which was used in this example, withrespect to the vacuum level is −4.94 [eV] as described above, the HOMOlevel of 2DBTCzPA-II was calculated as follows: −4.94−0.81=−5.75 [eV].

Example 11 Synthesis Example 9

In this example is described a method of synthesizing3,6-bis(dibenzofuran-4-yl)-9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole(abbreviation: DBF2CzPA-II), which is the carbazole derivativerepresented by the structural formula (601) in Embodiment 1. A structureof DBF2CzPA-II is illustrated in the following structural formula.

Step 1: Synthesis of 3,6-Di(benzofuran-4-yl)-9H-carbazole (abbreviation:DBF2Cz-II)

This was synthesized as in Example 7.

Step 2: Synthesis of3,6-Bis(dibenzofuran-4-yl)-9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole(abbreviation: DBF2CzPA-II)

To a 100-mL three-neck flask were added 0.99 g (2.4 mmol) of9-(4-bromophenyl)-10-phenylanthracene, 1.2 g (2.4 mmol) of3,6-bis(dibenzofuran-4-yl)-9H-carbazole, and 0.62 g (6.4 mmol) of sodiumtert-butoxide. After the air in the flask was replaced with nitrogen, tothis mixture were added 20 mL of toluene and 0.2 mL oftri(tert-butyl)phosphine (a 10 wt % hexane solution). This mixture wasdegassed by being stirred while the pressure was reduced. After thedegassing, 62 mg (0.11 mmol) of bis(dibenzylideneacetone)palladium(0)was added to the mixture. This mixture was stirred at 110° C. for 20hours under a nitrogen stream. After the stirring, 100 mL of toluene wasadded to the obtained mixture, and the mixture was suction-filteredthrough Celite (produced by Wako Pure Chemical Industries, Ltd., CatalogNo. 531-16855), alumina, and Florisil (produced by Wako Pure ChemicalIndustries, Ltd., Catalog No. 540-00135). The oily substance obtained byconcentration of the filtrate was recrystallized from toluene/hexane, sothat 1.2 g of a yellow solid was obtained in 59% yield. The synthesisscheme of Step 2 is illustrated in (b-8).

By a train sublimation method, the obtained yellow solid was purified.The purification was conducted by heating of 1.2 g of the yellow solidat 385° C. under a pressure of 2.6 Pa with a flow rate of argon gas of 5mL/min. After the purification, 0.73 g of a yellow solid was obtained in61% yield.

The yellow solid after the above purification was subjected to nuclearmagnetic resonance (NMR) spectroscopy. The measurement result isdescribed below.

¹H NMR (CDCl₃, 300 MHz):δ=7.36-7.55 (m, 12H), 7.58-7.67 (m, 5H),7.76-7.82 (m, 6H), 7.89 (d, J, =8.4 Hz, 4H), 7.95-8.00 (m, 4H),8.02-8.05 (m, 2H), 8.28 (dd, J₁=1.5 Hz, J₂=8.7 Hz, 2H), 8.81 (d, J₁=1.5Hz, 2H)

In addition, ¹H NMR charts are shown in FIGS. 35A and 35B. Note thatFIG. 35B is a chart where the range of from 7 ppm to 9 ppm in FIG. 35Ais enlarged. The measurement results showed that DBF2CzPA-II, which isthe carbazole derivative represented by the above structural formula,was obtained.

Next, an absorption and emission spectra of DBF2CzPA-II in a toluenesolution of DBF2CzPA-II are shown in FIG. 36A, and an absorption andemission spectra of a thin film of DBF2CzPA-II are shown in FIG. 36B. Anultraviolet-visible spectrophotometer (V-550, manufactured by JASCOCorporation) was used for the measurements of the absorption spectra. Inthe case of the toluene solution, the measurements were made with thetoluene solution of DBF2CzPA-II put in a quartz cell, and the absorptionspectrum obtained by subtraction of absorption spectra of the quartzcell and toluene from the measured spectrum is shown in the drawing. Inaddition, as for the absorption spectrum of the thin film, a sample wasprepared by evaporation of DBF2CzPA-II on a quartz substrate, and theabsorption spectrum obtained by subtraction of an absorption spectrum ofquartz from the absorption spectrum of this sample is shown in thedrawing. As in the measurements of the absorption spectra, anultraviolet-visible spectrophotometer (V-550, manufactured by JASCOCorporation) was used for the measurements of the emission spectra. Theemission spectrum of toluene was measured with the toluene solution ofDBF2CzPA-II put in a quartz cell, and the emission spectrum of the thinfilm was measured with a sample prepared by evaporation of DBF2CzPA-IIon a quartz substrate. Thus, it was found that the absorption peakwavelengths of DBF2CzPA-II in the toluene solution of DBF2CzPA-II werearound 396 nm, around 376 nm, around 357 nm, around 326 nm, and around291 nm, and the emission peak wavelength thereof was around 424 nm (atan excitation wavelength of 376 nm), and that the absorption peakwavelengths of the thin film of DBF2CzPA-II were around 402 nm, around381 nm, around 357 nm, around 325 nm, around 293 nm, and around 260 nmand the emission peak wavelengths thereof were around 542 nm and around447 nm (at an excitation wavelength of 403 nm).

Further, the ionization potential of DBF2CzPA-II in a thin film statewas measured by a photoelectron spectrometer (AC-2, manufactured byRiken Keiki, Co., Ltd.) in air. The obtained value of the ionizationpotential was converted to a negative value, so that the HOMO level ofDBF2CzPA-II was −5.74 eV. From the data of the absorption spectra of thethin film in FIG. 36B, the absorption edge of DBF2CzPA-II, which wasobtained from Tauc plot with an assumption of direct transition, was2.91 eV. Therefore, the optical energy gap of DBF2CzPA-II in the solidstate was estimated at 2.91 eV; from the values of the HOMO levelobtained above and this energy gap, the LUMO level of DBF2CzPA-II wasable to be estimated at −2.83 eV. It was thus found that DBF2CzPA-II hada wide energy gap of 2.91 eV in the solid state.

Further, the oxidation reaction characteristics of DBF2CzPA-II weremeasured. The oxidation reaction characteristics were examined by cyclicvoltammetry (CV) measurements. Note that an electrochemical analyzer(ALS model 600A or 600C, manufactured by BAS Inc.) was used for themeasurements.

For a solution for the CV measurements, dehydrated N,N-dimethylformamide(DMF, product of Sigma-Aldrich Inc., 99.8%, catalog No. 22705-6) wasused as a solvent, and tetra-n-butylammonium perchlorate (n-Bu₄NClO₄,product of Tokyo Chemical Industry Co., Ltd., catalog No. T0836), whichwas a supporting electrolyte, was dissolved in the solvent such that theconcentration thereof was 100 mmol/L. Further, the object to be measuredwas also dissolved in the solvent such that the concentration thereofwas 2 mmol/L. A platinum electrode (a PTE platinum electrode, product ofBAS Inc.) was used as a working electrode; a platinum electrode (a VC-3Pt counter electrode (5 cm), product of BAS Inc.) was used as anauxiliary electrode; and an Ag/Ag⁺ electrode (an RE5 nonaqueous solventreference electrode, product of BAS Inc.) was used as a referenceelectrode. Note that the measurements were conducted at room temperature(20° C. to 25° C.). The scan rates for the CV measurements wereuniformly set to 0.1 V/s.

In the measurements, scanning in which the potential of the workingelectrode with respect to the reference electrode was changed from 0.08V to 0.90 V and then changed from 0.90 V to 0.08 V was one cycle, and100 cycles were performed.

The measurement results revealed that DBF2CzPA-II showed propertieseffective against repetition of redox reactions between an oxidizedstate and a neutral state without a large variation in oxidation peakeven after the 100 cycles in the measurements.

Further, the HOMO level of DBF2CzPA-II was determined also bycalculation from the CV measurement results.

First, the potential energy of the reference electrode with respect tothe vacuum level used was found to be −4.94 eV, as determined inExample 1. The oxidation peak potential E_(pa) of DBF2CzPA-II was 0.87V. In addition, the reduction peak potential E_(pc) thereof was 0.73 V.Therefore, a half-wave potential (an intermediate potential betweenE_(pa) and E_(pc)) can be calculated at 0.80 V. This means thatDBF2CzPA-II is oxidized by an electric energy of 0.80 [V vs. Ag/Ag⁺],and this energy corresponds to the HOMO level. Here, since the potentialenergy of the reference electrode, which was used in this example, withrespect to the vacuum level is −4.94 [eV] as described above, the HOMOlevel of DBF2CzPA-II was calculated as follows: −4.94−0.80=−5.74 [eV].

Example 12 Synthesis Example 10

In this example is described a method of synthesizing3-(dibenzothiophen-4-yl)-9-[3-(10-phenyl-9-anthryl)phenyl]-9H-carbazole(abbreviation: mDBTCzPA-II), which is the carbazole derivativerepresented by the structural formula (335) in Embodiment 1. A structureof mDBTCzPA-II is illustrated in the following structural formula.

Step 1: Synthesis of 3-(Dibenzothiophen-4-yl)-9H-carbazole(abbreviation: DBTCz-II)

This was synthesized as in Step 1 in Example 1.

Step 2: Synthesis of3-(Dibenzothiophen-4-yl)-9-[3-(10-phenyl-9-anthryl)phenyl]-9H-carbazole(abbreviation: mDBTCzPA-II)

In a 50-mL three-neck flask were put 1.2 g (3.0 mmol) of9-(3-bromophenyl)-10-phenylanthracene, 1.1 g (3.0 mmol) of3-(dibenzothiophen-4-yl)-9H-carbazole, and 0.87 g (9.1 mmol) of sodiumtert-butoxide. After the air in the flask was replaced with nitrogen, tothis mixture were added 20 mL of toluene and 0.2 mL oftri(tert-butyl)phosphine (a 10 wt % hexane solution). This mixture wasdegassed by being stirred while the pressure was reduced. After thedegassing, 87 mg (0.15 mmol) of bis(dibenzylideneacetone)palladium(0)was added to this mixture. This mixture was stirred at 110° C. for 5hours under a nitrogen stream. After the stirring, the obtained mixturewas suction-filtered through Celite (produced by Wako Pure ChemicalIndustries, Ltd., Catalog No. 531-16855), alumina, and Florisil(produced by Wako Pure Chemical Industries, Ltd., Catalog No.540-00135). The filtrate was concentrated to give a yellow solid. Theobtained solid was recrystallized from toluene. The obtained crystal waspurified by high performance liquid column chromatography (abbreviation:HPLC) (developing solvent: chloroform). The obtained fraction wasconcentrated to give 1.5 g of a pale yellow solid in 72% yield. Thesynthesis scheme of Step 2 is illustrated in (b-9).

By a train sublimation method, the obtained pale yellow solid waspurified. The purification was conducted by heating of 1.0 g of the paleyellow solid at 300° C. under a pressure of 2.6 Pa with a flow rate ofargon gas of 5 mL/min. After the purification, 0.79 g of a white solidwas obtained in a yield of 79%.

The pale yellow solid after the above purification was subjected tonuclear magnetic resonance (NMR) spectroscopy. The measurement data areshown below.

¹H NMR (CDCl₃, 300 MHz):δ=7.30-7.52 (m, 10H), 7.55-7.68 (m, 7H),7.71-7.77 (m, 3H), 7.81-7.92 (m, 7H), 8.14-8.23 (m, 3H), 8.51 (d,J₁=0.90 Hz, 1H)

In addition, ¹H NMR charts are shown in FIGS. 37A and 37B. Note thatFIG. 37B is a chart where the range of from 7 ppm to 9 ppm in FIG. 37Ais enlarged. The measurement results showed that mDBTCzPA-II, which isthe carbazole derivative represented by the above structural formula,was obtained.

Next, an absorption and emission spectra of mDBTCzPA-II in a toluenesolution of mDBTCzPA-II are shown in FIG. 38A, and an absorption andemission spectra of a thin film of mDBTCzPA-II are shown in FIG. 38B. Anultraviolet-visible spectrophotometer (V-550, manufactured by JASCOCorporation) was used for the measurements of the absorption spectra. Inthe case of the toluene solution, the measurements were made with thetoluene solution of mDBTCzPA-II put in a quartz cell, and the absorptionspectrum obtained by subtraction of the absorption spectra of the quartzcell and toluene from the measured spectrum is shown in the drawing. Inaddition, as for the absorption spectrum of the thin film, a sample wasprepared by evaporation of mDBTCzPA-II on a quartz substrate, and theabsorption spectrum obtained by subtraction of an absorption spectrum ofquartz from the absorption spectrum of this sample is shown in thedrawing. As in the measurements of the absorption spectra, anultraviolet-visible spectrophotometer (V-550, manufactured by JASCOCorporation) was used for the measurements of the emission spectra. Theemission spectrum of toluene was measured with the toluene solution ofmDBTCzPA-II put in a quartz cell, and the emission spectrum of the thinfilm was measured with a sample prepared by evaporation of mDBTCzPA-IIon a quartz substrate. Thus, it was found that the absorption peakwavelengths of mDBTCzPA-II in the toluene solution of mDBTCzPA-II werearound 396 nm, around 375 nm, around 354 nm, around 336 nm, and around290 nm and the emission peak wavelengths thereof were around 412 nm andaround 433 nm (at an excitation wavelength of 376 nm), and that theabsorption peak wavelengths of the thin film of mDBTCzPA-II were around402 nm, around 381 nm, around 359 nm, around 340 nm, around 291 nm,around 261 nm, and around 207 nm and the greatest emission wavelengththereof was around 443 nm (at an excitation wavelength of 402 nm).

Further, the ionization potential of mDBTCzPA-II in a thin film statewas measured by a photoelectron spectrometer (AC-2, manufactured byRiken Keiki, Co., Ltd.) in air. The obtained value of the ionizationpotential was converted to a negative value, so that the HOMO level ofmDBTCzPA-II was −5.77 eV. From the data of the absorption spectra of thethin film in FIG. 38B, the absorption edge of mDBTCzPA-II, which wasobtained from Tauc plot with an assumption of direct transition, was2.95 eV. Therefore, the optical energy gap of mDBTCzPA-II in the solidstate was estimated at 2.95 eV; from the values of the HOMO levelobtained above and this energy gap, the LUMO level of mDBTCzPA-II wasable to be estimated at −2.82 eV. It was thus found that mDBTCzPA-II hada wide energy gap of 2.95 eV in the solid state.

Further, the oxidation reaction characteristics of mDBTCzPA-II weremeasured. The oxidation reaction characteristics were examined by cyclicvoltammetry (CV) measurements. Note that an electrochemical analyzer(ALS model 600A or 600C, manufactured by BAS Inc.) was used for themeasurements.

For a solution for the CV measurements, dehydrated N,N-dimethylformamide(DMF, product of Sigma-Aldrich Inc., 99.8%, catalog No. 22705-6) wasused as a solvent, and tetra-n-butylammonium perchlorate (n-Bu₄NClO₄,product of Tokyo Chemical Industry Co., Ltd., catalog No. T0836), whichwas a supporting electrolyte, was dissolved in the solvent such that theconcentration thereof was 100 mmol/L. Further, the object to be measuredwas also dissolved in the solvent such that the concentration thereofwas 2 mmol/L. A platinum electrode (a PTE platinum electrode, product ofBAS Inc.) was used as a working electrode; a platinum electrode (a VC-3Pt counter electrode (5 cm), product of BAS Inc.) was used as anauxiliary electrode; and an Ag/Ag⁺ electrode (an RE5 nonaqueous solventreference electrode, product of BAS Inc.) was used as a referenceelectrode. Note that the measurements were conducted at room temperature(20° C. to 25° C.). The scan rates for the CV measurements wereuniformly set to 0.1 V/s.

In the measurements, scanning in which the potential of the workingelectrode with respect to the reference electrode was changed from −0.04V to 1.15 V and then changed from 1.15 V to −0.04 V was one cycle, and100 cycles were performed.

The measurement results revealed that mDBTCzPA-II showed propertieseffective against repetition of redox reactions between an oxidizedstate and a neutral state without a large variation in oxidation peakeven after the 100 cycles in the measurements.

Further, the HOMO level of mDBTCzPA-II was determined also bycalculation from the CV measurement results.

First, the potential energy of the reference electrode with respect tothe vacuum level used was found to be −4.94 eV, as determined inExample 1. The oxidation peak potential E_(pa) of mDBTCzPA-II was 0.95V. In addition, the reduction peak potential E_(pc) thereof was 0.83 V.Therefore, a half-wave potential (an intermediate potential betweenE_(pa) and E_(pc)) can be calculated at 0.89 V. This means thatmDBTCzPA-II is oxidized by an electric energy of 0.89 [V versus Ag/Ag⁺],and this energy corresponds to the HOMO level. Here, since the potentialenergy of the reference electrode, which was used in this example, withrespect to the vacuum level is −4.94 [eV] as described above, the HOMOlevel of mDBTCzPA-II was calculated as follows: −4.94−0.89=−5.83 [eV].

Example 13 Synthesis Example 11

In this example is described a method of synthesizing3-(dibenzofuran-4-yl)-9-[3-(10-phenyl-9-anthryl)phenyl]-9H-carbazole(abbreviation: mDBFCzPA-II), which is the carbazole derivativerepresented by the structural formula (734) in Embodiment 1. A structureof mDBFCzPA-II is illustrated in the following structural formula.

Step 1: Synthesis of 3-(Dibenzofuran-4-yl)-9H-carbazole (abbreviation:DBFCz-II)

This was synthesized as in Step 1 in Example 2.

Step 2: Synthesis of3-(Dibenzofuran-4-yl)-9-[3-(10-phenyl-9-anthryl)phenyl]-9H-carbazole(abbreviation: mDBFCzPA-II)

In a 100-mL three-neck flask were put 1.2 g (3.0 mmol) of9-(3-bromophenyl)-10-phenylanthracene, 1.0 g (3.0 mmol) of3-(dibenzofuran-4-yl)-9H-carbazole, and 0.87 g (9.1 mmol) of sodiumtert-butoxide. After the air in the flask was replaced with nitrogen, tothis mixture were added 20 mL of toluene and 0.2 mL oftri(tert-butyl)phosphine (a 10 wt % hexane solution). This mixture wasdegassed by being stirred while the pressure was reduced. After thedegassing, 87 mg (0.15 mmol) of bis(dibenzylideneacetone)palladium(0)was added to this mixture. This mixture was stirred at 110° C. for 6hours under a nitrogen stream. After the stirring, the obtained mixturewas suction-filtered through Celite (produced by Wako Pure ChemicalIndustries, Ltd., Catalog No. 531-16855), alumina, and Florisil(produced by Wako Pure Chemical Industries, Ltd., Catalog No.540-00135). The filtrate was concentrated to give a yellow solid. Theobtained solid was recrystallized from toluene to give 1.8 g of a whitesolid which was the object of the synthesis in 88% yield. The synthesisscheme of Step 2 is illustrated in (b-10).

By a train sublimation method, the obtained white solid was purified.The purification was conducted by heating of 1.2 g of the white solid at300° C. under a pressure of 2.6 Pa with a flow rate of argon gas of 5mL/min. After the purification, 1.1 g of a white solid was obtained in ayield of 89%.

The white solid after the above purification was subjected to nuclearmagnetic resonance (NMR) spectroscopy. The measurement data are shownbelow.

¹H NMR (CDCl₃, 300 MHz):δ=7.31-7.40 (m, 4H), 7.42-7.67 (m, 13H),7.70-7.81 (m, 5H), 7.85-7.92 (m, 4H), 7.95 (dd, J₁=1.5 Hz, J₂=7.8 Hz,1H), 7.99-8.03 (m, 2H), 8.24 (d, J₁=7.8 Hz, 1H), 8.65 (d, J₁=1.5 Hz, 1H)

In addition, ¹H NMR charts are shown in FIGS. 39A and 39B. Note thatFIG. 39B is a chart where the range of from 7 ppm to 9 ppm in FIG. 39Ais enlarged. The measurement results showed that mDBFCzPA-II, which isthe carbazole derivative represented by the above structural formula,was obtained.

Next, an absorption and emission spectra of mDBFCzPA-II in a toluenesolution of mDBFCzPA-II are shown in FIG. 40A, and an absorption andemission spectra of a thin film of mDBFCzPA-II are shown in FIG. 40B. Anultraviolet-visible spectrophotometer (V-550, manufactured by JASCOCorporation) was used for the measurements of the absorption spectra. Inthe case of the toluene solution, the measurements were made with thetoluene solution of mDBFCzPA-II put in a quartz cell, and the absorptionspectrum obtained by subtraction of the absorption spectra of the quartzcell and toluene from the measured spectrum is shown in the drawing. Inaddition, as for the absorption spectrum of the thin film, a sample wasprepared by evaporation of mDBFCzPA-II on a quartz substrate, and theabsorption spectrum obtained by subtraction of an absorption spectrum ofquartz from the absorption spectrum of this sample is shown in thedrawing. As in the measurements of the absorption spectra, anultraviolet-visible spectrophotometer (V-550, manufactured by JASCOCorporation) was used for the measurements of the emission spectra. Theemission spectrum of toluene was measured with the toluene solution ofmDBFCzPA-II put in a quartz cell, and the emission spectrum of the thinfilm was measured with a sample prepared by evaporation of mDBFCzPA-IIon a quartz substrate. Thus, it was found that the absorption peakwavelengths of mDBFCzPA-II in the toluene solution of mDBFCzPA-II werearound 396 nm, around 375 nm, around 354 nm, around 336 nm, and around290 nm and the emission peak wavelengths thereof were around 412 nm andaround 433 nm (at an excitation wavelength of 375 nm), and that theabsorption peak wavelengths of the thin film of mDBFCzPA-II were around402 nm, around 381 nm, around 359 nm, around 340 nm, around 291 nm,around 261 nm, and around 207 nm and the greatest emission wavelengththereof was around 443 nm (at an excitation wavelength of 402 nm).

Further, the ionization potential of mDBFCzPA-II in a thin film statewas measured by a photoelectron spectrometer (AC-2, manufactured byRiken Keiki, Co., Ltd.) in air. The obtained value of the ionizationpotential was converted to a negative value, so that the HOMO level ofmDBFCzPA-II was −5.77 eV. From the data of the absorption spectra of thethin film in FIG. 40B, the absorption edge of mDBFCzPA-II, which wasobtained from Tauc plot with an assumption of direct transition, was2.95 eV. Therefore, the optical energy gap of mDBFCzPA-II in the solidstate was estimated at 2.95 eV; from the values of the HOMO levelobtained above and this energy gap, the LUMO level of mDBFCzPA-II wasable to be estimated at −2.82 eV. It was thus found that mDBFCzPA-II hada wide energy gap of 2.95 eV in the solid state.

Further, the oxidation reaction characteristics of mDBFCzPA-II weremeasured. The oxidation reaction characteristics were examined by cyclicvoltammetry (CV) measurements. Note that an electrochemical analyzer(ALS model 600A or 600C, manufactured by BAS Inc.) was used for themeasurements.

For a solution for the CV measurements, dehydrated N,N-dimethylformamide(DMF, product of Sigma-Aldrich Inc., 99.8%, catalog No. 22705-6) wasused as a solvent, and tetra-n-butylammonium perchlorate (n-Bu₄NClO₄,product of Tokyo Chemical Industry Co., Ltd., catalog No. T0836), whichwas a supporting electrolyte, was dissolved in the solvent such that theconcentration thereof was 100 mmol/L. Further, the object to be measuredwas also dissolved in the solvent such that the concentration thereofwas 2 mmol/L. A platinum electrode (a PTE platinum electrode, product ofBAS Inc.) was used as a working electrode; a platinum electrode (a VC-3Pt counter electrode (5 cm), product of BAS Inc.) was used as anauxiliary electrode; and an Ag/Ag⁺ electrode (an RE5 nonaqueous solventreference electrode, product of BAS Inc.) was used as a referenceelectrode. Note that the measurements were conducted at room temperature(20° C. to 25° C.). The scan rates for the CV measurements wereuniformly set to 0.1 V/s.

In the measurements, scanning in which the potential of the workingelectrode with respect to the reference electrode was changed from −0.04V to 1.15 V and then changed from 1.15 V to −0.04 V was one cycle, and100 cycles were performed.

The measurement results revealed that mDBFCzPA-II showed propertieseffective against repetition of redox reactions between an oxidizedstate and a neutral state without a large variation in oxidation peakeven after the 100 cycles in the measurements.

Further, the HOMO level of mDBFCzPA-II was determined also bycalculation from the CV measurement results.

First, the potential energy of the reference electrode with respect tothe vacuum level used was found to be −4.94 eV, as determined inExample 1. The oxidation peak potential E_(pa) of mDBFCz-PA-II was 0.95V. In addition, the reduction peak potential E_(pc) thereof was 0.83 V.Therefore, a half-wave potential (an intermediate potential betweenE_(pa) and E_(pc)) can be calculated at 0.89 V. This means thatmDBFCzPA-II is oxidized by an electric energy of 0.89 [V versus Ag/Ag⁺],and this energy corresponds to the HOMO level. Here, since the potentialenergy of the reference electrode, which was used in this example, withrespect to the vacuum level is −4.94 [eV] as described above, the HOMOlevel of mDBFCzPA-II was calculated as follows: −4.94−0.89=−5.83 [eV].

Example 14 synthesis example 12

In this example is described a method of synthesizing3-(6-phenyldibenzothiophen-4-yl)-9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole(abbreviation: DBTCzPA-IV), which is the carbazole derivativerepresented by the structural formula (203) in Embodiment 1. A structureof DBTCzPA-IV is illustrated in the following structural formula.

Step 1: Synthesis of 3-(6-Phenyldibenzothiophen-4-yl)-9H-carbazole(abbreviation: DBTCz-IV)

In a 50-mL three-neck flask were put 1.0 g (4.1 mmol) of3-bromocarbazole, 1.2 g (4.1 mmol) of 6-phenyl-4-dibenzothienylboronicacid, and 62 mg (0.20 mmol) of tris(2-methylphenyl)phosphine. To thismixture were added 15 mL of toluene, 5 mL of ethanol, and 5 mL of a 2.0M aqueous sodium carbonate solution. This mixture was degassed by beingstirred while the pressure was reduced. To this mixture was added 9 mg(0.041 mmol) of palladium(II) acetate, and the mixture was stirred at80° C. for 3 hours under a nitrogen stream. After the stirring, theaqueous layer of this mixture was subjected to extraction with toluene,and the solution of the extract and the organic layer were combined andwashed with saturated brine. The organic layer was dried over magnesiumsulfate. This mixture was separated by gravity filtration, and thefiltrate was concentrated to give a solid. This solid was purified bysilica gel column chromatography (developing solvent, toluene:hexane=1:2and then toluene:hexane=3:2). Addition of ethyl acetate/hexane to theobtained solid was followed by irradiation with ultrasonic waves, andthe solid was collected by suction filtration, so that 1.0 g of a whitesolid which was the object of the synthesis in 59% yield. The synthesisscheme of Step 1 is illustrated in (a-11).

The obtained white solid was subjected to nuclear magnetic resonance(NMR) spectroscopy. The measurement data are shown below.

¹H NMR (CDCl₃, 300 MHz):δ=7.34-7.55 (m, 7H), 7.56 (d, J₁=4.2 Hz, 1H),7.58-7.64 (m, 3H), 7.68-7.72 (m, 2H), 7.78 (dd, J, =1.8 Hz, J₂=8.4 Hz,1H), 8.10 (dd, =0.90 Hz, J₂=1.8 Hz, 1H), 8.15 (s, 1H), 8.19-8.23 (m,2H), 8.36 (d, J₁=1.5 Hz, 1H)

In addition, ¹H NMR charts are shown in FIGS. 41A and 41B. Note thatFIG. 41B is a chart where the range of from 7 ppm to 8.5 ppm in FIG. 41Ais enlarged. The measurement results showed that DBTCz-IV, which is thecarbazole derivative represented by the above structural formula, wasobtained.

Step 2: Synthesis of3-(6-Phenyldibenzothiophen-4-yl)-9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole(abbreviation: DBTCzPA-IV)

In a 50-mL three-neck flask were put 1.3 g (3.3 mmol) of9-(4-bromophenyl)-10-phenylanthracene, 1.0 g (2.4 mmol) of3-(6-phenyldibenzothiophen-4-yl)-9H-carbazole, and 0.95 g (9.9 mmol) ofsodium tert-butoxide. After the air in the flask was replaced withnitrogen, to this mixture were added 20 mL of toluene and 0.2 mL oftri(tert-butyl)phosphine (a 10 wt % hexane solution). This mixture wasdegassed by being stirred while the pressure was reduced. After thedegassing, 11 mg (0.18 mmol) of bis(dibenzylideneacetone)palladium(0)was added to this mixture. This mixture was stirred at 110° C. for 6hours under a nitrogen stream. After the stirring, the aqueous layer ofthis mixture was subjected to extraction with toluene, and the solutionof the extract and the organic layer were combined and washed withsaturated brine. The organic layer was dried over magnesium sulfate.This mixture was gravity-filtered, and the filtrate was concentrated togive a solid. The obtained solid was purified by silica gel columnchromatography (developing solvent, toluene:hexane=1:9 and thentoluene:hexane=3:7). The obtained solid was recrystallized fromtoluene/hexane to give 1.4 g of a pale yellow solid which was the objectof the synthesis in a yield of 80%. The synthesis scheme of Step 2 isillustrated in (b-11).

By a train sublimation method, 1.4 g of the obtained pale yellow solidwas purified. The purification was conducted by heating of the paleyellow solid at 360° C. under a pressure of 2.9 Pa with a flow rate ofargon gas of 5 mL/min. After the purification, 1.2 g of a pale yellowsolid was obtained in a yield of 86%.

The pale yellow solid after the above purification was subjected tonuclear magnetic resonance (NMR) spectroscopy. The measurement data areshown below.

¹H NMR (CDCl₃, 300 MHz):δ=7.34-7.49 (m, 9H), 7.51-7.54 (in, 3H), 7.57(t, J₁=1.5 Hz, 1H), 7.59-7.66 (m, 5H), 7.67-7.80 (m, 8H), 7.84-7.90 (m,5H), 8.22-8.25 (m, 3H), 8.49 (d, J₁=1.5 Hz, 1H)

In addition, ¹H NMR charts are shown in FIGS. 42A and 42B. Note thatFIG. 42B is a chart where the range of from 7 ppm to 9 ppm in FIG. 42Ais enlarged. The measurement results showed that DBTCzPA-IV, which isthe carbazole derivative represented by the above structural formula,was obtained.

Next, an absorption and emission spectra of DBTCzPA-IV in a toluenesolution of DBTCzPA-IV are shown in FIG. 43A, and an absorption andemission spectra of a thin film of DBTCzPA-IV are shown in FIG. 43B. Anultraviolet-visible spectrophotometer (V-550, manufactured by JASCOCorporation) was used for the measurements of the absorption spectra. Inthe case of the toluene solution, the measurements were made with thetoluene solution of DBTCzPA-IV put in a quartz cell, and the absorptionspectrum obtained by subtraction of the absorption spectra of the quartzcell and toluene from the measured spectrum is shown in the drawing. Inaddition, as for the absorption spectrum of the thin film, a sample wasprepared by evaporation of DBTCzPA-IV on a quartz substrate, and theabsorption spectrum obtained by subtraction of an absorption spectrum ofquartz from the absorption spectrum of this sample is shown in thedrawing. As in the measurements of the absorption spectra, anultraviolet-visible spectrophotometer (V-550, manufactured by JASCOCorporation) was used for the measurements of the emission spectra. Theemission spectrum of toluene was measured with the toluene solution ofDBTCzPA-IV put in a quartz cell, and the emission spectrum of the thinfilm was measured with a sample prepared by evaporation of DBTCzPA-IV ona quartz substrate. Thus, it was found that the absorption peakwavelengths of DBTCzPA-IV in the toluene solution of DBTCzPA-IV werearound 396 nm, around 376 nm, around 340 nm, and around 281 nm and theemission peak wavelengths thereof were around 423 nm and around 437 nm(at an excitation wavelength of 376 nm), and that the absorption peakwavelengths of the thin film of DBTCzPA-IV were around 403 nm, around382 nm, around 356 nm, around 345 nm, around 296 nm, and around 264 nmand the greatest emission wavelength thereof was around 443 nm (at anexcitation wavelength of 403 nm).

Further, the ionization potential of DBTCzPA-IV in a thin film state wasmeasured by a photoelectron spectrometer (AC-2, manufactured by RikenKeiki, Co., Ltd.) in air. The obtained value of the ionization potentialwas converted to a negative value, so that the HOMO level of DBTCzPA-IVwas −5.80 eV. From the data of the absorption spectra of the thin filmin FIG. 43B, the absorption edge of DBTCzPA-IV, which was obtained fromTauc plot with an assumption of direct transition, was 2.93 eV.Therefore, the optical energy gap of DBTCzPA-IV in the solid state wasestimated at 2.93 eV; from the values of the HOMO level obtained aboveand this energy gap, the LUMO level of DBTCzPA-IV was able to beestimated at −2.87 eV. It was thus found that DBTCzPA-IV had a wideenergy gap of 2.93 eV in the solid state.

Further, the oxidation reaction characteristics of DBTCzPA-IV weremeasured. The oxidation reaction characteristics were examined by cyclicvoltammetry (CV) measurements. Note that an electrochemical analyzer(ALS model 600A or 600C, manufactured by BAS Inc.) was used for themeasurements.

For a solution for the CV measurements, dehydrated N,N-dimethylformamide(DMF, product of Sigma-Aldrich Inc., 99.8%, catalog No. 22705-6) wasused as a solvent, and tetra-n-butylammonium perchlorate (n-Bu₄NClO₄,product of Tokyo Chemical Industry Co., Ltd., catalog No. T0836), whichwas a supporting electrolyte, was dissolved in the solvent such that theconcentration thereof was 100 mmol/L. Further, the object to be measuredwas also dissolved in the solvent such that the concentration thereofwas 2 mmol/L. A platinum electrode (a PTE platinum electrode, product ofBAS Inc.) was used as a working electrode; a platinum electrode (a VC-3Pt counter electrode (5 cm), product of BAS Inc.) was used as anauxiliary electrode; and an Ag/Ag⁺ electrode (an RE5 nonaqueous solventreference electrode, product of BAS Inc.) was used as a referenceelectrode. Note that the measurements were conducted at room temperature(20° C. to 25° C.). The scan rates for the CV measurements wereuniformly set to 0.1 V/s.

In the measurements, scanning in which the potential of the workingelectrode with respect to the reference electrode was changed from −0.02V to 0.93 V and then changed from 0.93 V to −0.02 V was one cycle, and100 cycles were performed.

The measurement results revealed that DBTCzPA-IV showed propertieseffective against repetition of redox reactions between an oxidizedstate and a neutral state without a large variation in oxidation peakeven after the 100 cycles in the measurements.

Further, the HOMO level of DBTCzPA-W was determined also by calculationfrom the CV measurement results.

First, the potential energy of the reference electrode with respect tothe vacuum level used was found to be −4.94 eV, as determined inExample 1. The oxidation peak potential E_(pa) of DBTCzPA-IV was 0.89 V.In addition, the reduction peak potential E_(pc) thereof was 0.79 V.Therefore, a half-wave potential (an intermediate potential betweenE_(pa) and E_(pc)) can be calculated at 0.84 V. This means thatDBTCzPA-IV is oxidized by an electric energy of 0.84 [V versus Ag/Ag⁺],and this energy corresponds to the HOMO level. Here, since the potentialenergy of the reference electrode, which was used in this example, withrespect to the vacuum level is −4.94 [eV] as described above, the HOMOlevel of DBTCzPA-IV was calculated as follows: −4.94−0.84=−5.78.

Example 15 Synthesis Example 13

In this example is described a method of synthesizing3-(dibenzothiophen-4-yl)-9-[4-(9,10-diphenyl-2-anthryl)phenyl]-9H-carbazole(abbreviation: 2DBTCzPPA-II), which is the carbazole derivativerepresented by the structural formula (323) in Embodiment 1. A structureof 2DBTCzPPA-II is illustrated in the following structural formula.

Step 1: Synthesis of 3-(Dibenzothiophen-4-yl)-9H-carbazole (abbreviation

DBTCz-II))

This was synthesized as in Step 1 in Example 1.

Step 2: Synthesis of3-(Dibenzothiophen-4-yl)-9-[4-(9,10-diphenyl-2-anthryl)phenyl]-9H-carbazole(abbreviation: 2DBTCzPPA-II)

In a 50-mL three-neck flask were put 1.3 g (2.7 mmol) of2-(4-bromophenyl)-9,10-diphenylanthracene, 0.93 g (2.7 mmol) of3-(dibenzothiophen-4-yl)-9H-carbazole, and 0.76 g (8.0 mmol) of sodiumtert-butoxide. After the air in the flask was replaced with nitrogen, tothis mixture were added 20 mL of toluene and 0.2 mL oftri(tert-butyl)phosphine (a 10 wt % hexane solution). This mixture wasdegassed by being stirred while the pressure was reduced. After thedegassing, 76 mg (0.13 mmol) of bis(dibenzylideneacetone)palladium(0)was added to this mixture. This mixture was stirred at 110° C. for 4hours under a nitrogen stream. After the stirring, the obtained mixturewas suction-filtered through Celite (produced by Wako Pure ChemicalIndustries, Ltd., Catalog No. 531-16855), alumina, and Florisil(produced by Wako Pure Chemical Industries, Ltd., Catalog No.540-00135), and the filtrate was concentrated to give a solid. Theobtained solid was purified by silica gel column chromatography(developing solvent, hexane:toluene=5:1). A suspension was formed byaddition of toluene/hexane to the obtained solid, and the suspension wasirradiated with ultrasonic waves. Then, a solid was collected by suctionfiltration, so that 1.2 g of a yellow solid which was the object of thesynthesis was obtained in a yield of 61%. The synthesis scheme of Step 2is illustrated in (b-12).

By a train sublimation method, the obtained yellow solid was purified.The purification was conducted by heating of 1.2 g of the yellow solidat 335° C. under a pressure of 2.6 Pa with a flow rate of argon gas of 5mL/min. After the purification, 1.01 g of a yellow solid was obtained ina yield of 83%.

The yellow solid after the above purification was subjected to nuclearmagnetic resonance (NMR) spectroscopy. The measurement data are shownbelow.

¹H NMR (CDCl₃, 300 MHz):δ=7.29-7.39 (m, 3H), 7.41-7.51 (m, 4H),7.52-7.75 (m, 18H), 7.78-7.88 (m, 5H), 8.03 (d, J₁=1.5 Hz, 1H),8.15-8.23 (m, 3H), 8.51 (d, J₁=0.90 Hz, 1H)

In addition, ¹H NMR charts are shown in FIGS. 44A and 44B. Note thatFIG. 44B is a chart where the range of from 7 ppm to 9 ppm in FIG. 44Ais enlarged. The measurement results showed that 2DBTCzPPA-II, which isthe carbazole derivative represented by the above structural formula,was obtained.

Next, an absorption and emission spectra of 2DBTCzPPA-II in a toluenesolution of 2DBTCzPPA-II are shown in FIG. 45A, and an absorption andemission spectra of a thin film of 2DBTCzPPA-II are shown in FIG. 45B.An ultraviolet-visible spectrophotometer (V-550, manufactured by JASCOCorporation) was used for the measurements of the absorption spectra. Inthe case of the toluene solution, the measurements were made with thetoluene solution of 2DBTCzPPA-II put in a quartz cell, and theabsorption spectrum obtained by subtraction of the absorption spectra ofthe quartz cell and toluene from the measured spectrum is shown in thedrawing. In addition, as for the absorption spectrum of the thin film, asample was prepared by evaporation of 2DBTCzPPA-II on a quartzsubstrate, and the absorption spectrum obtained by subtraction of anabsorption spectrum of quartz from the absorption spectrum of thissample is shown in the drawing. As in the measurements of the absorptionspectra, an ultraviolet-visible spectrophotometer (V-550, manufacturedby JASCO Corporation) was used for the measurements of the emissionspectra. The emission spectrum of toluene was measured with the toluenesolution of 2DBTCzPPA-II put in a quartz cell, and the emission spectrumof the thin film was measured with a sample prepared by evaporation of2DBTCzPPA-II on a quartz substrate. Thus, it was found that theabsorption peak wavelengths of 2DBTCzPPA-II in the toluene solution of2DBTCzPPA-II were around 404 nm, around 382 nm, around 336 nm, andaround 285 nm and the emission peak wavelengths thereof were around 483nm, around 452 nm, and around 427 nm (at an excitation wavelength of 387nm), and that the absorption peak wavelengths of the thin film of2DBTCzPPA-II were around 415 nm, around 393 nm, around 346 nm, around291 nm, and around 244 nm and the emission peak wavelengths thereof werearound 461 nm and around 442 nm (at an excitation wavelength of 415 nm).

Further, the ionization potential of 2DBTCzPPA-II in a thin film statewas measured by a photoelectron spectrometer (AC-2, manufactured byRiken Keiki, Co., Ltd.) in air. The obtained value of the ionizationpotential was converted to a negative value, so that the HOMO level of2DBTCzPPA-II was −5.70 eV. From the data of the absorption spectra ofthe thin film in FIG. 45B, the absorption edge of 2DBTCzPPA-II, whichwas obtained from Tauc plot with an assumption of direct transition, was2.81 eV. Therefore, the optical energy gap of 2DBTCzPPA-II in the solidstate was estimated at 2.81 eV; from the values of the HOMO levelobtained above and this energy gap, the LUMO level of 2DBTCzPPA-II wasable to be estimated at −2.89 eV. It was thus found that 2DBTCzPPA-IIhad a wide energy gap of 2.81 eV in the solid state.

Further, the oxidation reaction characteristics of 2DBTCzPPA-II weremeasured. The oxidation reaction characteristics were examined by cyclicvoltammetry (CV) measurements. Note that an electrochemical analyzer(ALS model 600A or 600C, manufactured by BAS Inc.) was used for themeasurements.

For a solution for the CV measurements, dehydrated N,N-dimethylformamide(DMF, product of Sigma-Aldrich Inc., 99.8%, catalog No. 22705-6) wasused as a solvent, and tetra-n-butylammonium perchlorate (n-Bu₄NClO₄,product of Tokyo Chemical Industry Co., Ltd., catalog No. T0836), whichwas a supporting electrolyte, was dissolved in the solvent such that theconcentration thereof was 100 mmol/L. Further, the object to be measuredwas also dissolved in the solvent such that the concentration thereofwas 2 mmol/L. A platinum electrode (a PTE platinum electrode, product ofBAS Inc.) was used as a working electrode; a platinum electrode (a VC-3Pt counter electrode (5 cm), product of BAS Inc.) was used as anauxiliary electrode; and an Ag/Ag⁺ electrode (an RE5 nonaqueous solventreference electrode, product of BAS Inc.) was used as a referenceelectrode. Note that the measurements were conducted at room temperature(20° C. to 25° C.). The scan rates for the CV measurements wereuniformly set to 0.1 V/s.

In the measurements, scanning in which the potential of the workingelectrode with respect to the reference electrode was changed from 0.31V to 0.92 V and then changed from 0.92 V to 0.31 V was one cycle, and100 cycles were performed.

The measurement results revealed that 2DBTCzPPA-II showed propertieseffective against repetition of redox reactions between an oxidizedstate and a neutral state without a large variation in oxidation peakeven after the 100 cycles in the measurements.

Further, the HOMO level of 2DBTCzPPA-II was determined also bycalculation from the CV measurement results.

First, the potential energy of the reference electrode with respect tothe vacuum level used was found to be −4.94 eV, as determined inExample 1. The oxidation peak potential E_(pa) of 2DBTCzPPA-II was 0.88V. In addition, the reduction peak potential E_(pc) thereof was 0.80 V.Therefore, a half-wave potential (an intermediate potential betweenE_(pa) and E_(pc)) can be calculated at 0.84 V. This means that2DBTCzPPA-II is oxidized by an electric energy of 0.84 [V versusAg/Ag⁺], and this energy corresponds to the HOMO level. Here, since thepotential energy of the reference electrode, which was used in thisexample, with respect to the vacuum level is −4.94 [eV] as describedabove, the HOMO level of 2DBTCzPPA-II was calculated as follows:−4.94−0.84=−5.78 [eV].

Example 16 Synthesis Example 14

In this example is described a method of synthesizing3-(dibenzofuran-4-yl)-9-[4-(9,10-diphenyl-2-anthryl)phenyl]-9H-carbazole(abbreviation: 2DBFCzPPA-II), which is the carbazole derivativerepresented by the structural formula (719) in Embodiment 1. A structureof 2DBFCzPPA-II is illustrated in the following structural formula.

Step 1: Synthesis of 3-(Dibenzofuran-4-yl)-9H-carbazole (abbreviation:DBFCz-II)

This was synthesized as in Step 1 in Example 2.

Step 2: Synthesis of3-(Dibenzofuran-4-yl)-9-[4-(9,10-diphenyl-2-anthryflphenyl]-9H-carbazole(abbreviation: 2DBFCzPPA-II)

In a 50-mL three-neck flask were put 1.3 g (2.7 mmol) of2-(4-bromophenyl)-9,10-diphenylanthracene, 0.88 g (2.7 mmol) of3-(dibenzofuran-4-yl)-9H-carbazole, and 0.76 g (8.0 mmol) of sodiumtert-butoxide. After the air in the flask was replaced with nitrogen, tothis mixture were added 20 mL of toluene and 0.2 mL oftri(tert-butyl)phosphine (a 10 wt % hexane solution). This mixture wasdegassed by being stirred while the pressure was reduced. After thedegassing, 76 mg (0.13 mmol) of bis(dibenzylideneacetone)palladium(0)was added to this mixture. This mixture was stirred at 110° C. for 4hours under a nitrogen stream. After the stirring, the obtained mixturewas suction-filtered through Celite (produced by Wako Pure ChemicalIndustries, Ltd., Catalog No. 531-16855), alumina, and Florisil(produced by Wako Pure Chemical Industries, Ltd., Catalog No.540-00135), and the filtrate was concentrated to give a solid. Thissolid was purified by silica gel column chromatography (developingsolvent, hexane:toluene=5:1). This solid was purified by highperformance liquid column chromatography (abbreviation: HPLC)(developing solvent: chloroform). The obtained fraction was concentratedto give 1.4 g of a yellow solid which was the object of the synthesis in71% yield. The synthesis scheme of Step 2 is illustrated in (b-13).

By a train sublimation method, the obtained yellow solid was purified.The purification was conducted by heating of 0.90 g of the yellow solidat 360° C. under a pressure of 2.6 Pa with a flow rate of argon gas of 5mL/min. After the purification, 0.73 g of a yellow solid was obtained ina yield of 81%.

The yellow solid after the above purification was subjected to nuclearmagnetic resonance (NMR) spectroscopy. The measurement data are shownbelow.

¹H NMR (CDCl₃, 300 MHz):δ=7.30-7.42 (m, 4H), 7.45-7.52 (m, 4H),7.53-7.75 (m, 18H), 7.78-7.88 (m, 3H), 7.93-8.03 (m, 4H), 8.24 (d,J₁=7.5 Hz, 1H), 8.66 (d, J₁=1.5 Hz, 1H)

In addition, ¹H NMR charts are shown in FIGS. 46A and 46B. Note thatFIG. 46B is a chart where the range of from 7 ppm to 9 ppm in FIG. 46Ais enlarged. The measurement results showed that 2DBFCzPPA-II, which isthe carbazole derivative represented by the above structural formula,was obtained.

Next, an absorption and emission spectra of 2DBFCzPPA-II in a toluenesolution of 2DBFCzPPA-II are shown in FIG. 47A, and an absorption andemission spectra of a thin film of 2DBFCzPPA-II are shown in FIG. 47B.An ultraviolet-visible spectrophotometer (V-550, manufactured by JASCOCorporation) was used for the measurements of the absorption spectra. Inthe case of the toluene solution, the measurements were made with thetoluene solution of 2DBFCzPPA-II put in a quartz cell, and theabsorption spectrum obtained by subtraction of the absorption spectra ofthe quartz cell and toluene from the measured spectrum is shown in thedrawing. In addition, as for the absorption spectrum of the thin film, asample was prepared by evaporation of 2DBFCzPPA-II on a quartzsubstrate, and the absorption spectrum obtained by subtraction of anabsorption spectrum of quartz from the absorption spectrum of thissample is shown in the drawing. As in the measurements of the absorptionspectra, an ultraviolet-visible spectrophotometer (V-550, manufacturedby JASCO Corporation) was used for the measurements of the emissionspectra. The emission spectrum of toluene was measured with the toluenesolution of 2DBFCzPPA-II put in a quartz cell, and the emission spectrumof the thin film was measured with a sample prepared by evaporation of2DBFCzPPA-II on a quartz substrate. Thus, it was found that theabsorption peak wavelengths of 2DBFCzPPA-II in the toluene solution of2DBFCzPPA-II were around 403 nm, around 381 nm, around 336 nm, andaround 284 nm and the emission peak wavelengths thereof were around 453nm and around 427 nm (at an excitation wavelength of 387 nm), and thatthe absorption peak wavelengths of the thin film of 2DBFCzPPA-II werearound 415 nm, around 392 nm, around 347 nm, around 291 nm, and around254 nm and the greatest emission wavelengths thereof were around 461 nmand around 443 nm (at an excitation wavelength of 415 nm).

Further, the ionization potential of 2DBFCzPPA-II in a thin film statewas measured by a photoelectron spectrometer (AC-2, manufactured byRiken Keiki, Co., Ltd.) in air. The obtained value of the ionizationpotential was converted to a negative value, so that the HOMO level of2DBFCzPPA-II was −5.68 eV. From the data of the absorption spectra ofthe thin film in FIG. 47B, the absorption edge of 2DBFCzPPA-II, whichwas obtained from Tauc plot with an assumption of direct transition, was2.81 eV. Therefore, the optical energy gap of 2DBFCzPPA-II in the solidstate was estimated at 2.81 eV; from the values of the HOMO levelobtained above and this energy gap, the LUMO level of 2DBFCzPPA-II wasable to be estimated at −2.87 eV. It was thus found that 2DBFCzPPA-IIhad a wide energy gap of 2.81 eV in the solid state.

Further, the oxidation reaction characteristics of 2DBFCzPPA-II weremeasured. The oxidation reaction characteristics were examined by cyclicvoltammetry (CV) measurements. Note that an electrochemical analyzer(ALS model 600A or 600C, manufactured by BAS Inc.) was used for themeasurements.

For a solution for the CV measurements, dehydrated N,N-dimethylformamide(DMF, product of Sigma-Aldrich Inc., 99.8%, catalog No. 22705-6) wasused as a solvent, and tetra-n-butylammonium perchlorate (n-Bu₄NClO₄,product of Tokyo Chemical Industry Co., Ltd., catalog No. T0836), whichwas a supporting electrolyte, was dissolved in the solvent such that theconcentration thereof was 100 mmol/L. Further, the object to be measuredwas also dissolved in the solvent such that the concentration thereofwas 2 mmol/L. A platinum electrode (a PTE platinum electrode, product ofBAS Inc.) was used as a working electrode; a platinum electrode (a VC-3Pt counter electrode (5 cm), product of BAS Inc.) was used as anauxiliary electrode; and an Ag/Ag⁺ electrode (an RE5 nonaqueous solventreference electrode, product of BAS Inc.) was used as a referenceelectrode. Note that the measurements were conducted at room temperature(20° C. to 25° C.). The scan rates for the CV measurements wereuniformly set to 0.1 V/s.

In the measurements, scanning in which the potential of the workingelectrode with respect to the reference electrode was changed from 0.27V to 0.90 V and then changed from 0.90 V to 0.26 V was one cycle, and100 cycles were performed.

The measurement results revealed that 2DBFCzPPA-II showed propertieseffective against repetition of redox reactions between an oxidizedstate and a neutral state without a large variation in oxidation peakeven after the 100 cycles in the measurements.

Further, the HOMO level of 2DBFCzPPA-II was determined also bycalculation from the CV measurement results.

First, the potential energy of the reference electrode with respect tothe vacuum level used was found to be −4.94 eV, as determined inExample 1. The oxidation peak potential E_(pa) of 2DBFCzPPA-II was 0.89V. In addition, the reduction peak potential E_(pc) thereof was 0.75 V.Therefore, a half-wave potential (an intermediate potential betweenE_(pa) and E_(pc)) can be calculated at 0.82 V. This means that2DBFCzPPA-II is oxidized by an electric energy of 0.82 [V versusAg/Ag⁺], and this energy corresponds to the HOMO level. Here, since thepotential energy of the reference electrode, which was used in thisexample, with respect to the vacuum level is −4.94 [eV] as describedabove, the HOMO level of 2DBFCzPPA-II was calculated as follows:−4.94−0.82=−5.76 [eV].

Example 17 Synthesis Example 15

In this example is described a method of synthesizing3-(dibenzothiophen-4-yl)-9-[3-(9,10-diphenyl-2-anthryl)phenyl]-9H-carbazole(abbreviation: 2mDBTCzPPA-II), which is the carbazole derivativerepresented by the structural formula (324) in Embodiment 1. A structureof 2mDBTCzPPA-II is illustrated in the following structural formula.

Step 1: Synthesis of 3-(Dibenzothiophen-4-yl)-9H-carbazole(abbreviation: DBTCz-II)

This was synthesized as in Step 1 in Example 1.

Step 2: Synthesis of3-(Dibenzothiophen-4-yl)-9-[3-(9,10-diphenyl-2-anthryl)phenyl]-9H-carbazole(abbreviation: 2mDBTCzPPA-II)

In a 100-mL three-neck flask were put 1.0 g (2.1 mmol) of2-(3-bromophenyl)-9,10-diphenylanthracene, 0.72 g (2.1 mmol) of3-(dibenzothiophen-4-yl)-9H-carbazole, and 0.59 g (6.2 mmol) of sodiumtert-butoxide. After the air in the flask was replaced with nitrogen, tothis mixture were added 20 mL of toluene and 0.2 mL oftri(tert-butyl)phosphine (a 10 wt % hexane solution). This mixture wasdegassed by being stirred while the pressure was reduced. After thedegassing, 59 mg (0.10 mmol) of bis(dibenzylideneacetone)palladium(0)was added to this mixture. This mixture was stirred at 110° C. for 5hours under a nitrogen stream. After the stirring, the obtained mixturewas suction-filtered through Celite (produced by Wako Pure ChemicalIndustries, Ltd., Catalog No. 531-16855), alumina, and Florisil(produced by Wako Pure Chemical Industries, Ltd., Catalog No.540-00135). The filtrate was concentrated to give a yellow solid. Thissolid was purified by silica gel column chromatography (developingsolvent, hexane:toluene=5:1). The obtained solid was recrystallized fromtoluene/hexane to give 1.1 g of a yellow solid in 70% yield. Thesynthesis scheme of Step 2 is illustrated in (b-14).

By a train sublimation method, the obtained yellow solid was purified.The purification was conducted by heating of 1.1 g of the yellow solidat 330° C. under a pressure of 2.9 Pa with a flow rate of argon gas of 5mL/min. After the purification, 0.89 g of a yellow solid was obtained ina yield of 84%.

The yellow solid after the above purification was subjected to nuclearmagnetic resonance (NMR) spectroscopy. The measurement data are shownbelow.

¹H NMR (CDCl₃, 300 MHz):δ=7.30-7.38 (m, 3H), 7.40-7.76 (m, 23H),7.77-7.87 (m, 4H), 8.01 (d, J₁=0.90 Hz, 1H), 8.16-8.24 (m, 3H), 8.52 (d,J₁=1.2 Hz, 1H)

In addition, ¹H NMR charts are shown in FIGS. 48A and 48B. Note thatFIG. 48B is a chart where the range of from 7 ppm to 9 ppm in FIG. 48Ais enlarged. The measurement results showed that 2mDBTCzPPA-II, which isthe carbazole derivative represented by the above structural formula,was obtained.

Next, an absorption and emission spectra of 2mDBTCzPPA-II in a toluenesolution of 2mDBTCzPPA-II are shown in FIG. 49A, and an absorption andemission spectra of a thin film of 2mDBTCzPPA-II are shown in FIG. 49B.An ultraviolet-visible spectrophotometer (V-550, manufactured by JASCOCorporation) was used for the measurements of the absorption spectra. Inthe case of the toluene solution, the measurements were made with thetoluene solution of 2mDBTCzPPA-II put in a quartz cell, and theabsorption spectrum obtained by subtraction of the absorption spectra ofthe quartz cell and toluene from the measured spectrum is shown in thedrawing. In addition, as for the absorption spectrum of the thin film, asample was prepared by evaporation of 2mDBTCzPPA-II on a quartzsubstrate, and the absorption spectrum obtained by subtraction of anabsorption spectrum of quartz from the absorption spectrum of thissample is shown in the drawing. As in the measurements of the absorptionspectra, an ultraviolet-visible spectrophotometer (V-550, manufacturedby JASCO Corporation) was used for the measurements of the emissionspectra. The emission spectrum of toluene was measured with the toluenesolution of 2mDBTCzPPA-II put in a quartz cell, and the emissionspectrum of the thin film was measured with a sample prepared byevaporation of 2mDBTCzPPA-II on a quartz substrate. Thus, it was foundthat the absorption peak wavelengths of 2mDBTCzPPA-II in the toluenesolution of 2mDBTCzPPA-II were around 406 nm, around 385 nm, around 365nm, around 335 nm, and around 292 nm and the emission peak wavelengthsthereof were around 424 nm and around 437 nm (at an excitationwavelength of 385 nm), and that the absorption peak wavelengths of thethin film of 2mDBTCzPPA-II were around 414 nm, around 392 nm, around 370nm, around 339 nm, around 295 nm, around 245 nm, and around 208 nm andthe emission peak wavelengths thereof were around 492 nm, around 459 nm,and around 440 nm (at an excitation wavelength of 403 nm).

Further, the ionization potential of 2mDBTCzPPA-II in a thin film statewas measured by a photoelectron spectrometer (AC-2, manufactured byRiken Keiki, Co., Ltd.) in air. The obtained value of the ionizationpotential was converted to a negative value, so that the HOMO level of2mDBTCzPPA-II was −5.74 eV. From the data of the absorption spectra ofthe thin film in FIG. 49B, the absorption edge of 2mDBTCzPPA-II, whichwas obtained from Tauc plot with an assumption of direct transition, was2.84 eV. Therefore, the optical energy gap of 2mDBTCzPPA-II in the solidstate was estimated at 2.84 eV; from the values of the HOMO levelobtained above and this energy gap, the LUMO level of 2mDBTCzPPA-II wasable to be estimated at −2.90 eV. It was thus found that 2mDBTCzPPA-IIhad a wide energy gap of 2.84 eV in the solid state.

Further, the oxidation reaction characteristics of 2mDBTCzPPA-II weremeasured. The oxidation reaction characteristics were examined by cyclicvoltammetry (CV) measurements. Note that an electrochemical analyzer(ALS model 600A or 600C, manufactured by BAS Inc.) was used for themeasurements.

For a solution for the CV measurements, dehydrated N,N-dimethylformamide(DMF, product of Sigma-Aldrich Inc., 99.8%, catalog No. 22705-6) wasused as a solvent, and tetra-n-butylammonium perchlorate (n-Bu₄NClO₄,product of Tokyo Chemical Industry Co., Ltd., catalog No. T0836), whichwas a supporting electrolyte, was dissolved in the solvent such that theconcentration thereof was 100 mmol/L. Further, the object to be measuredwas also dissolved in the solvent such that the concentration thereofwas 2 mmol/L. A platinum electrode (a PTE platinum electrode, product ofBAS Inc.) was used as a working electrode; a platinum electrode (a VC-3Pt counter electrode (5 cm), product of BAS Inc.) was used as anauxiliary electrode; and an Ag/Ag⁺ electrode (an RE5 nonaqueous solventreference electrode, product of BAS Inc.) was used as a referenceelectrode. Note that the measurements were conducted at room temperature(20° C. to 25° C.). The scan rates for the CV measurements wereuniformly set to 0.1 V/s.

In the measurements, scanning in which the potential of the workingelectrode with respect to the reference electrode was changed from 0.06V to 1.05 V and then changed from 1.05 V to 0.06 V was one cycle, and100 cycles were performed.

The measurement results revealed that 2mDBTCzPPA-II showed propertieseffective against repetition of redox reactions between an oxidizedstate and a neutral state without a large variation in oxidation peakeven after the 100 cycles in the measurements.

Further, the HOMO level of 2mDBTCzPPA-II was determined also bycalculation from the CV measurement results.

First, the potential energy of the reference electrode with respect tothe vacuum level used was found to be −4.94 eV, as determined inExample 1. The oxidation peak potential E_(pa) of 2mDBTCzPPA-II was 0.91V. In addition, the reduction peak potential E_(pc) thereof was 0.82 V.Therefore, a half-wave potential (an intermediate potential betweenE_(pa) and E_(pc)) can be calculated at 0.87 V. This means that2mDBTCzPPA-II is oxidized by an electric energy of 0.87 [V versusAg/Ag⁺], and this energy corresponds to the HOMO level. Here, since thepotential energy of the reference electrode, which was used in thisexample, with respect to the vacuum level is −4.94 [eV] as describedabove, the HOMO level of 2mDBTCzPPA-II was calculated as follows:−4.94−0.87=−5.81 [eV].

Example 18 Synthesis Example 16

In this example is described a method of synthesizing3-(dibenzofuran-4-yl)-9-[3-(9,10-diphenyl-2-anthryl)phenyl]-9H-carbazole(abbreviation: 2mDBFCzPPA-II), which is the carbazole derivativerepresented by the structural formula (727) in Embodiment 1. A structureof 2mDBFCzPPA-II is illustrated in the following structural formula.

Step 1: Synthesis of 3-(Dibenzofuran-4-yl)-9H-carbazole (abbreviation:DBFCz-II)

This was synthesized as in Step 1 in Example 2.

Step 2: Synthesis of3-(Dibenzofuran-4-yl)-9-[3-(9,10-diphenyl-2-anthryl)phenyl]-9H-carbazole(abbreviation: 2mDBFCzPPA-II)

In a 100-mL three-neck flask were put 1.0 g (2.1 mmol) of2-(3-bromophenyl)-9,10-diphenylanthracene, 0.69 g (2.1 mmol) of3-(dibenzofuran-4-yl)-9H-carbazole, and 0.59 g (6.2 mmol) of sodiumtert-butoxide. After the air in the flask was replaced with nitrogen, tothis mixture were added 20 mL of toluene and 0.2 mL oftri(tert-butyl)phosphine (a 10 wt % hexane solution). This mixture wasdegassed by being stirred while the pressure was reduced. After thedegassing, 59 mg (0.10 mmol) of bis(dibenzylideneacetone)palladium(0)was added to this mixture. This mixture was stirred at 110° C. for 5hours under a nitrogen stream. After the stirring, the obtained mixturewas suction-filtered through Celite (produced by Wako Pure ChemicalIndustries, Ltd., Catalog No. 531-16855), alumina, and Florisil(produced by Wako Pure Chemical Industries, Ltd., Catalog No.540-00135). The filtrate was concentrated to give a yellow solid. Theobtained solid was recrystallized from toluene, and the obtained crystalwas purified by high performance liquid column chromatography(abbreviation: HPLC) (developing solvent: chloroform). The obtainedfraction was concentrated to give 0.91 g of a pale yellow solid in 60%yield. The synthesis scheme of Step 2 is illustrated in (b-15).

By a train sublimation method, the obtained pale yellow solid waspurified. The purification was conducted by heating of 0.90 g of thepale yellow solid at 335° C. under a pressure of 2.7 Pa with a flow rateof argon gas of 5 mL/min. After the purification, 0.78 g of a paleyellow solid was obtained in a yield of 87%.

The yellow solid after the above purification was subjected to nuclearmagnetic resonance (NMR) spectroscopy. The measurement data are shownbelow.

¹H NMR (CDCl₃, 300 MHz):δ=7.30-7.41 (m, 4H), 7.44-7.76 (m, 23H),7.81-7.85 (m, 2H), 7.95-8.05 (m, 4H), 8.25 (d, J₁=7.5 Hz, 1H), 8.66 (d,J₁=1.5 Hz, 1H)

In addition, ¹H NMR charts are shown in FIGS. 50A and 50B. Note thatFIG. 50B is a chart where the range of from 7 ppm to 9 ppm in FIG. 50Ais enlarged. The measurement results showed that 2mDBFCzPPA-II, which isthe carbazole derivative represented by the above structural formula,was obtained.

Next, an absorption and emission spectra of 2mDBFCzPPA-II in a toluenesolution of 2mDBFCzPPA-II are shown in FIG. 51A, and an absorption andemission spectra of a thin film of 2mDBFCzPPA-II are shown in FIG. 51B.An ultraviolet-visible spectrophotometer (V-550, manufactured by JASCOCorporation) was used for the measurements of the absorption spectra. Inthe case of the toluene solution, the measurements were made with thetoluene solution of 2mDBFCzPPA-II put in a quartz cell, and theabsorption spectrum obtained by subtraction of the absorption spectra ofthe quartz cell and toluene from the measured spectrum is shown in thedrawing. In addition, as for the absorption spectrum of the thin film, asample was prepared by evaporation of 2mDBFCzPPA-II on a quartzsubstrate, and the absorption spectrum obtained by subtraction of anabsorption spectrum of quartz from the absorption spectrum of thissample is shown in the drawing. As in the measurements of the absorptionspectra, an ultraviolet-visible spectrophotometer (V-550, manufacturedby JASCO Corporation) was used for the measurements of the emissionspectra. The emission spectrum of toluene was measured with the toluenesolution of 2mDBFCzPPA-II put in a quartz cell, and the emissionspectrum of the thin film was measured with a sample prepared byevaporation of 2mDBFCzPPA-II on a quartz substrate. Thus, it was foundthat the absorption peak wavelengths of 2mDBFCzPPA-II in the toluenesolution of 2mDBFCzPPA-II were around 406 nm, around 385 nm, around 365nm, and around 291 nm and the emission peak wavelengths thereof werearound 436 nm and around 424 nm (at an excitation wavelength of 386 nm),and that the absorption peak wavelengths of the thin film of2mDBFCzPPA-II were around 414 nm, around 391 nm, around 369 nm, around328 nm, around 294 nm, and around 252 nm and the emission peakwavelengths thereof were around 488 nm, around 457 nm, and around 438 nm(at an excitation wavelength of 413 nm).

Further, the ionization potential of 2mDBFCzPPA-II in a thin film statewas measured by a photoelectron spectrometer (AC-2, manufactured byRiken Keiki, Co., Ltd.) in air. The obtained value of the ionizationpotential was converted to a negative value, so that the HOMO level of2mDBFCzPPA-II was −5.75 eV. From the data of the absorption spectra ofthe thin film in FIG. 51B, the absorption edge of 2mDBFCzPPA-II, whichwas obtained from Tauc plot with an assumption of direct transition, was2.84 eV. Therefore, the optical energy gap of 2mDBFCzPPA-II in the solidstate was estimated at 2.84 eV; from the values of the HOMO levelobtained above and this energy gap, the LUMO level of 2mDBFCzPPA-II wasable to be estimated at −2.91 eV. It was thus found that 2mDBFCzPPA-IIhad a wide energy gap of 2.84 eV in the solid state.

Further, the oxidation reaction characteristics of 2mDBFCzPPA-II weremeasured. The oxidation reaction characteristics were examined by cyclicvoltammetry (CV) measurements. Note that an electrochemical analyzer(ALS model 600A or 600C, manufactured by BAS Inc.) was used for themeasurements.

For a solution for the CV measurements, dehydrated N,N-dimethylformamide(DMF, product of Sigma-Aldrich Inc., 99.8%, catalog No. 22705-6) wasused as a solvent, and tetra-n-butylammonium perchlorate (n-Bu₄NClO₄,product of Tokyo Chemical Industry Co., Ltd., catalog No. T0836), whichwas a supporting electrolyte, was dissolved in the solvent such that theconcentration thereof was 100 mmol/L. Further, the object to be measuredwas also dissolved in the solvent such that the concentration thereofwas 2 mmol/L. A platinum electrode (a PTE platinum electrode, product ofBAS Inc.) was used as a working electrode; a platinum electrode (a VC-3Pt counter electrode (5 cm), product of BAS Inc.) was used as anauxiliary electrode; and an Ag/Ag⁺ electrode (an RE5 nonaqueous solventreference electrode, product of BAS Inc.) was used as a referenceelectrode. Note that the measurements were conducted at room temperature(20° C. to 25° C.). The scan rates for the CV measurements wereuniformly set to 0.1 V/s.

In the measurements, scanning in which the potential of the workingelectrode with respect to the reference electrode was changed from −0.41V to 1.05 V and then changed from 1.05 V to −1.41 V was one cycle, and100 cycles were performed.

The measurement results revealed that 2mDBFCzPPA-II showed propertieseffective against repetition of redox reactions between an oxidizedstate and a neutral state without a large variation in oxidation peakeven after the 100 cycles in the measurements.

Further, the HOMO level of 2mDBFCzPPA-II was determined also bycalculation from the CV measurement results.

First, the potential energy of the reference electrode with respect tothe vacuum level used was found to be −4.94 eV, as determined inExample 1. The oxidation peak potential E_(pa) of 2mDBFCzPPA-II was 0.93V. In addition, the reduction peak potential E_(pc) thereof was 0.82 V.Therefore, a half-wave potential (an intermediate potential betweenE_(pa) and E_(pc)) can be calculated at 0.88 V. This means that2mDBFCzPPA-II is oxidized by an electric energy of 0.88 [V versusAg/Ag⁺], and this energy corresponds to the HOMO level. Here, since thepotential energy of the reference electrode, which was used in thisexample, with respect to the vacuum level is −4.94 [eV] as describedabove, the HOMO level of 2mDBFCzPPA-II was calculated as follows:−4.94−0.88=−5.82 [eV].

Reference Example 1

A method of synthesizingN,N′-bis[4-(9-phenyl-9H-fluoren-9-yl)phenyl]-N,N′-diphenyl-pyrene-1,6-diamine(abbreviation: 1,6FLPAPrn) (structural formula (vi)) used in the aboveExamples is specifically described. A structure of 1,6FLPAPrn isillustrated below.

Step 1: Method of Synthesizing 9-(4-Bromophenyl)-9-phenylfluorene

In a 100-mL three-neck flask, 1.2 g (50 mmol) of magnesium was heatedand stirred for 30 minutes under reduced pressure to be activated. Theactivated magnesium was cooled to room temperature, and the flask wasmade to contain a nitrogen atmosphere. Then, several drops ofdibromoethane were added, so that foam formation and heat generationwere confirmed. After 12 g (50 mmol) of 2-bromobiphenyl dissolved in 10mL of diethyl ether was slowly added dropwise to this mixture, themixture was heated and stirred under reflux for 2.5 hours, so that aGrignard reagent was prepared.

Into a 500-mL three-neck flask were placed 10 g (40 mmol) of4-bromobenzophenone and 100 mL of diethyl ether, and the air in theflask was replaced with nitrogen. After the Grignard reagent which wassynthesized in advance was slowly added dropwise to this mixture, themixture was heated and stirred under reflux for 9 hours.

After reaction, this mixture solution was filtered to give a residue.The obtained residue was dissolved in 150 mL of ethyl acetate, and 1 Mhydrochloric acid was added thereto until acidification, and thenstirring was performed for 2 hours. The organic layer of this mixturewas washed with water, and dried by addition of magnesium sulfate. Thismixture was filtered, and the obtained filtrate was concentrated to givean oily substance.

Into a 500-mL recovery flask were placed this oily substance, 50 mL ofglacial acetic acid, and 1.0 mL of hydrochloric acid. The mixture wasstirred and heated at 130° C. for 1.5 hours under a nitrogen atmosphere.

After the reaction, this reaction mixture was filtered to give aresidue. The obtained residue was washed with water, an aqueous sodiumhydroxide solution, water, and methanol in this order. Then, the mixturewas dried, so that the substance which was the object of the synthesiswas obtained as 11 g of a white powder in 69% yield. The synthesisscheme of the above Step 1 is illustrated in (E1-1) below.

Step 2: Method of Synthesizing 4-(9-Phenyl-9H-fluoren-9-yl)diphenylamine(abbreviation: FLPA)

In a 200-mL three-neck flask were put 5.8 g (14.6 mmol) of9-(4-bromophenyl)-9-phenylfluorene, 1.7 mL (18.6 mmol) of aniline, and4.2 g (44.0 mmol) of sodium tert-butoxide. The air in the flask wasreplaced with nitrogen. To this mixture were added 147.0 mL of tolueneand 0.4 mL of a 10% hexane solution of tri(tert-butyl)phosphine. Thetemperature of this mixture was set to 60° C., and 66.1 mg (0.1 mmol) ofbis(dibenzylideneacetone)palladium(0) was added to the mixture, followedby stirring for 3.5 hours. After the stirring, the mixture wassuction-filtered through Florisil (produced by Wako Pure ChemicalIndustries, Ltd., Catalog No. 540-00135), Celite (produced by Wako PureChemical Industries, Ltd., Catalog No. 531-16855), and alumina. Theobtained filtrate was concentrated. The solid obtained by concentrationof the obtained filtrate was purified by silica gel columnchromatography (developing solvent, hexane:toluene=2:1). The obtainedfraction was concentrated to give 6.0 g of a white solid in 99% yield,which was the object of the synthesis. The synthesis scheme of Step 2 isillustrated in (E1-2) below.

Step 3: Method of SynthesizingN,N′-Bis[4-(9-phenyl-9H-fluoren-9-yl)phenyl]-N,N′-diphenyl-pyrene-1,6-diamine(abbreviation: 1,6FLPAPrn)

In a 50-mL three-neck flask were put 0.4 g (1.2 mmol) of1,6-dibromopyrene, 1.0 g (2.4 mmol) of4-(9-phenyl-9H-fluoren-9-yl)diphenylamine (abbreviation: FLPA), whichwas obtained in Step 2 in Reference Example 1, and 0.3 g (3.6 mmol) ofsodium tert-butoxide. The air in the flask was replaced with nitrogen.To this mixture were added 11.5 mL of toluene and 0.20 mL of a 10%hexane solution of tri(tert-butyl)phosphine. The temperature of thismixture was set to 70° C., and 31.1 mg (0.05 mmol) ofbis(dibenzylideneacetone)palladium(0) was added to the mixture, followedby stirring for 4.0 hours. After the stirring, the mixture wassuction-filtered through Florisil, Celite, and alumina, and a filtratewas obtained. The obtained filtrate was concentrated. The solid obtainedby concentration of the obtained filtrate was purified by silica gelcolumn chromatography (developing solvent: chloroform). The obtainedfraction was concentrated to give a yellow solid. The obtained solid waswashed with a mixed solvent of toluene and hexane, and then the mixturewas suction-filtered to give a yellow solid. The obtained yellow solidwas washed with a mixed solvent of chloroform and hexane, so that 0.8 gof a pale yellow powdered solid was obtained in 68% yield.

By a train sublimation method, 0.8 g of the obtained pale yellow solidwas purified. Under a pressure of 2.7 Pa with a flow rate of argon gasat 5.0 mL/min, the sublimation purification was carried out at 360° C.After the purification, 0.4 g of the object of the synthesis wasobtained in a yield of 56%. The synthesis scheme of Step 3 isillustrated in (E2-A) below.

A nuclear magnetic resonance (NMR) method and a mass spectrometryidentified the obtained compound asN,N′-bis[4-(9-phenyl-9H-fluoren-9-yl)phenyl]-N,N′-diphenyl-pyrene-1,6-diamine(abbreviation: 1,6FLPAPrn). The ¹H NMR data is shown below.

¹H NMR (CDCl₃, 300 MHz):δ=6.88-6.91 (m, 6H), 7.00-7.03 (m, 8H),7.13-7.40 (m, 26H), 7.73-7.80 (m, 6H), 7.87 (d, J=9.0 Hz, 2H), 8.06-8.09(m, 4H)

Reference Example 2

A method of synthesizing4-phenyl-4′-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: BPAFLP)(structural formula (i)) used in the above Example is specificallydescribed. A structure of BPAFLP is illustrated below.

Step 1: Synthesis of 9-(4-Bromophenyl)-9-phenylfluorene

This was synthesized as in Step 1 in Reference Example 1.

Step 2: Synthesis of 4-Phenyl-4′-(9-phenylfluoren-9-yl)triphenylamine(abbreviation: BPAFLP)

Into a 100-mL three-neck flask were placed 3.2 g (8.0 mmol) of9-(4-bromophenyl)-9-phenylfluorene, 2.0 g (8.0 mmol) of4-phenyl-diphenylamine, 1.0 g (10 mmol) of sodium tert-butoxide, and 23mg (0.04 mmol) of bis(dibenzylideneacetone)palladium(0), and the air inthe flask was replaced with nitrogen. Then, 20 mL of dehydrated xylenewas added to this mixture. After the mixture was degassed by beingstirred under reduced pressure, 0.2 mL (0.1 mmol) oftri(tert-butyl)phosphine (a 10 wt % hexane solution) was added to themixture. This mixture was stirred and heated at 110° C. for 2 hoursunder a nitrogen atmosphere.

After the reaction, 200 mL of toluene was added to this reactionmixture, and this suspension was filtered through Florisil (produced byWako Pure Chemical Industries, Ltd., Catalog No. 540-00135) and Celite(produced by Wako Pure Chemical Industries, Ltd., Catalog No.531-16855). The obtained filtrate was concentrated, and the resultingsubstance was purified by silica gel column chromatography (developingsolvent, toluene:hexane=1:4). The obtained fraction was concentrated,and the resulting substance was recrystallized from acetone/methanol, sothat the substance which was the object of the synthesis was obtained as4.1 g of a white powder in 92% yield. A reaction scheme of the abovesynthesis method is illustrated in (J-4) below.

The Rf values of the substance that was the object of the synthesis,9-(4-bromophenyl)-9-phenylfluorene, and 4-phenyl-diphenylamine wererespectively 0.41, 0.51, and 0.27, which were found by silica gel thinlayer chromatography (TLC) (developing solvent, ethyl acetate:hexane=1:10).

The compound obtained in the above Step 2 was subjected to nuclearmagnetic resonance (NMR) spectroscopy. The measurement data are shownbelow. The measurement results indicate that the obtained compound wasBPAFLP, which is a fluorene derivative.

¹H NMR (CDCl₃, 300 MHz):δ (ppm)=6.63-7.02 (m, 3H), 7.06-7.11 (m, 6H),7.19-7.45 (m, 18H), 7.53-7.55 (m, 2H), 7.75 (d, J=6.9, 2H)

REFERENCE NUMERALS

-   101: substrate, 102: first electrode, 103: layer containing organic    compound, 104: second electrode, 111: hole-injection layer, 112:    hole-transport layer, 113: light-emitting layer, 114:    electron-transport layer, 501: first electrode, 502: second    electrode, 511: first light-emitting unit, 512: second    light-emitting unit, 513: charge generation layer, 601: driver    circuit portion: (source-side driver circuit), 602: pixel portion,    603: driver circuit portion: (gate-side driver circuit), 604:    sealing substrate, 605: sealing material, 607: space, 608: wiring,    609: FPC (flexible printed circuit), 610: element substrate, 611:    switching TFT, 612: current controlling TFT, 613: first electrode,    614: insulator, 616: layer containing organic compound, 617: second    electrode, 618: light-emitting element, 623: n-channel TFT, 624:    p-channel TFT, 901: housing, 902: liquid crystal layer, 903:    backlight, 904: housing, 905: driver IC, 906: terminal, 951:    substrate, 952: electrode, 953: insulating layer, 954: partition    layer, 955: a layer containing organic compound, 956: electrode,    1201: source electrode, 1202: active layer, 1203: drain electrode,    1204: gate electrode, 2001: housing, 2002: light source, 3001:    lighting device, 9101: housing, 9102: support, 9103: display    portion, 9104: speaker portion, 9105: video input terminal, 9201:    main body, 9202: housing, 9203: display portion, 9204: keyboard,    9205: external connection port, 9206: pointing device, 9401: main    body, 9402: housing, 9403: display portion, 9404: audio input    portion, 9405: audio output portion, 9406: operation key, 9407:    external connection port, 9408: antenna, 9501: main body, 9502:    display portion, 9503: housing, 9504: external connection port,    9505: remote control receiving portion, 9506: image receiving    portion, 9507: battery, 9508: audio input portion, 9509: operation    key, 9510: eye piece portion.

This application is based on Japanese Patent Application serial no.2010-211184 filed with Japan Patent Office on Sep. 21, 2010, andJapanese Patent Application serial no. 2011-182368 filed with JapanPatent Office on Aug. 24, 2011, the entire contents of which are herebyincorporated by reference.

What is claimed is:
 1. A method for synthesizing an organic compound,the method including: conducting a reaction of an aryl halide with acarbazole derivative represented by the following formula (1):

wherein: X¹ represents sulfur; X² represents oxygen or sulfur; R¹ to R⁷and R⁹ to R¹⁵ individually represent hydrogen, an alkyl group having 1to 4 carbon atoms, or an aryl group having 6 to 15 carbon atoms; thearyl halide has 14 to 70 carbon atoms, and the aryl halide is reactedwith 9-position of a carbazolyl group of the carbazole derivative. 2.The method according to claim 1, wherein the carbazole derivative isrepresented by any one of the following formulae:


3. The method according to claim 1, wherein the aryl halide isrepresented by a halogen atom bonded to an aromatic ring, and whereinthe aromatic ring is a condensed tricyclic ring, a condensed tetracyclicring, a condensed pentacyclic ring, a condensed hexacyclic ring, or acondensed heptacyclic ring.
 4. The method according to claim 1, wherein:the aryl halide is represented by the following formula:Ar-X⁵; X⁵ represents halogen; and Ar represents an aryl group having 14to 70 carbon atoms.
 5. The method according to claim 4, wherein the arylhalide includes an aromatic ring and halogen atom bonded to the aromaticring, and wherein the aromatic ring is a condensed tricyclic ring, acondensed tetracyclic ring, a condensed pentacyclic ring, a condensedhexacyclic ring, or a condensed heptacyclic ring.
 6. The methodaccording to claim 4, wherein Ar is represented by any one of thefollowing formulae:


7. The method according to claim 1, wherein R¹ to R⁷ and R⁹ to R¹⁵individually are represented by any one of the following formulae:


8. The method according to claim 1, wherein the following formulaseparated from the formula (1) is reacted with 2-position of thecarbazolyl group of the carbazole derivative or 3-position of thecarbazolyl group of the carbazole derivative:


9. The method according to claim 8, wherein the following formulaseparated from the formula (1) is reacted with 6-position of thecarbazolyl group of the carbazole derivative or 7-position of thecarbazolyl group of the carbazole derivative:


10. The method according to claim 1, wherein the following formulaeseparated from the formula (1) are the same as each other:


11. A method for synthesizing an organic compound, the method including:conducting a reaction according to the following scheme (B-1):

conducting a reaction according to the following scheme (B-2):

and conducting a reaction of an aryl halide with a carbazole derivativerepresented by the following formula (1):

wherein: X¹ represents sulfur; X² represents oxygen or sulfur; X⁴ and X⁸individually represent a boronic acid; X⁶ and X⁷ individually representhalogen or a triflate group; R¹ to R⁷ and R⁹ to R¹⁵ individuallyrepresent hydrogen, an alkyl group having 1 to 4carbon atoms, or an arylgroup having 6 to 15 carbon atoms; the aryl halide has 14 to 70 carbonatoms, and the aryl halide is reacted with 9-position of a carbazolylgroup of the carbazole derivative.
 12. The method according to claim 11,wherein the aryl halide is represented by a halogen atom bonded to anaromatic ring, and wherein the aromatic ring is a condensed tricyclicring, a condensed tetracyclic ring, a condensed pentacyclic ring, acondensed hexacyclic ring, or a condensed heptacyclic ring.
 13. Themethod according to claim 11, wherein: the aryl halide is represented bythe following formula:Ar-X⁵; X⁵ represents halogen; and Ar represents an aryl group having 14to 70 carbon atoms.
 14. The method according to claim 13, wherein thearyl halide includes an aromatic ring and halogen atom bonded to thearomatic ring, and wherein the aromatic ring is a condensed tricyclicring, a condensed tetracyclic ring, a condensed pentacyclic ring, acondensed hexacyclic ring, or a condensed heptacyclic ring.
 15. A methodfor synthesizing an organic compound, the method including: conducting areaction according to the following scheme (B-2):

and conducting a reaction of an aryl halide with a carbazole derivativerepresented by the following formula (1):

wherein: X¹ represents sulfur; X² represents oxygen or sulfur; X⁶represents halogen or a triflate group; X⁸ represents a boronic acid; R¹to R⁷ and R⁹ to R¹⁵ individually represent hydrogen, an alkyl grouphaving 1 to 4 carbon atoms, or an aryl group having 6 to 15 carbonatoms; the aryl halide has 14 to 70 carbon atoms, and the aryl halide isreacted with 9-position of a carbazolyl group of the carbazolederivative.
 16. The method according to claim 15, wherein the arylhalide is represented by a halogen atom bonded to an aromatic ring, andwherein the aromatic ring is a condensed tricyclic ring, a condensedtetracyclic ring, a condensed pentacyclic ring, a condensed hexacyclicring, or a condensed heptacyclic ring.
 17. The method according to claim15, wherein: the aryl halide is represented by the following formula:Ar-X⁵; X⁵ represents halogen; and Ar represents an aryl group having 14to 70 carbon atoms.
 18. The method according to claim 17, wherein thearyl halide includes an aromatic ring and halogen atom bonded to thearomatic ring, and wherein the aromatic ring is a condensed tricyclicring, a condensed tetracyclic ring, a condensed pentacyclic ring, acondensed hexacyclic ring, or a condensed heptacyclic ring.
 19. Themethod according to claim 1, before conducting the reaction of the arylhalide with the carbazole derivative, further comprising the step ofconducting a reaction of the carbazolyl group of the carbazolederivative with 4-position of the following formula separated from theformula (1):